Brad Pitt has reached a turning point. To the public he is one of Hollywood’s hottest actors. Together with wife Angelina Jolie he forms one of the most famous partnerships in the world. They are even a word in their own right: “Brangelina”. However, Pitt no longer wants to be seen as just eye candy. Can he makes us see him any differently?

We meet, waiting for a lift in a hotel in Deauville, France. Our rooms are next door to one another. Jolie is at Pitt’s side, sleek in black. She has just put the children to bed. He inquires affectionately if they are asleep. She replies that they are. The couple seem relaxed and happy.

Outside a milling crowd held back by a fully holstered squad of French police awaits their appearance.

Pitt starts talking about his new film The Assassination of Jesse James by the Coward Robert Ford, which is having its premiere at the town’s film festival. His role as James won him Best Actor at the Venice Film Festival.

“I hope they like the film,” he comments in his syrupy Missouri drawl, taking a sip from the glass of champagne that he’s holding, “because it is a really slow-burn picture. If you think this version is long, you should have seen the four-and-a-half-hour one. This is the fast-track one.”

This version is a mere two and a half hours long. It has taken Pitt about a decade to get it on the screen and he takes the role of Jesse James, the legendary 19th-century American outlaw, and is also one of the producers, with Ridley Scott.

“It’s a delicious film and it was a real joy for me because I really wanted to make it,” he tells me. “My choice to make it was not about how well it would do. Film-making is a crapshoot and as I don’t bet on the horses this is my gamble. It will find a time and place for itself. I believe all good films do. It will sit and breathe like a good wine. This film isn’t the popular version of the swash-buckling Jesse James. It’s more of a throwback to some of those complex, complicated films of the 1970s.

“It hasn’t got a lot of dialogue and is what our director [the New Zealander Andrew Dominik] calls ‘a plotless film with no nude scenes’! Everybody keeps asking where is the nude scene of me in the bath? We never shot one.”

The film is a poetic meditation on a murder and its consequences. It is set in the last year of James’s life, when he is planning his next great robbery and waging war on his enemies, who are trying to collect the reward money – and the glory – that is riding on his capture.

It is also a time when he and his young devotee, Robert Ford, played by Casey Affleck, the brother of Ben Affleck, had certain psychological scores to settle. The assassination happens in James’s own home, when he is shot in the back by “the coward” Ford, who harbours a grudge that his feelings for James have not been reciprocated. “James is at a point in his life when he feels psychologically bad about what he has to do to protect himself,” Pitt expands. “He is self-absorbed and he is almost the last figure of the ‘old’ America, living in the Robber State, Missouri, a state that people emigrating from East to West would skirt around. I’m actually from the same area in Missouri that he was. He lived in a changing America, with a lawless, unsettled country behind and a modern, electrified America with telephones, cars and a new government ahead.”

Pitt thinks James was “one of the first American superstars. There are aspects of his celebrity that I absolutely understand. One is the byproduct of celebrity – being hunted. He was a man hunted with a bounty on his head. That can happen to me but at least nobody is pointing a gun at me, as Robert Ford did at Jesse.”

Jesse James is Pitt’s 30th film, and he has come a long way from his middle-America beginnings: born in Oklahoma, growing up in Springfield, Missouri, where he went to the unlikely named Kicka-poo High School.

The son of a businessman in trucking, he’s the eldest of three in a close-knit, strict Baptist family. He is still very linked to his hometown, donating $100,000 (£49,000) to the Discovery Center, a children’s learning museum there.

Pitt first came to public attention in a 1991 Levi’s ad, and his gorgeous body was again famously on display as a sexy drifter in Thelma and Louisethe same year.

He has long since tempered his pin-up prettiness with muscles, fire and brimstone, in films that include playing the Greek warrior Achilles in a skirt in the swords-and-sandals epic-drama Troy, Fight Club, Seven, Snatch and the lively Mr & Mrs Smith with Jolie. They met on the set of the film, in which they played married assassins, in 2003. He was nominated for a Golden Globe for his performance in Legends of the Fall and won one for Twelve Monkeys (for which he was also Oscar nominated).

Now, at 43, he has his own family, a daughter with Jolie, and is father to her three adopted children. “I think I’m about at the halfway mark now I am over 40,” he says. “I guess the direction gets clearer and the haze clears and you really focus on what you want to focus on as you get older.”

That would include carving a reputation as a respected producer, as with A Mighty Heart, starring Jolie as Mariane Pearl, the widow of the Wall Street Journal reporter Daniel Pearl, who was beheaded by jihadist militants while reporting in Karachi in 2002. James Christopher, The Times’s chief film critic, raved that Jolie’s performance as Mariane had “rigour and passion”.

“I was very taken with Mariane’s story, and Angelina knew her independently from me,” Pitt says. “It was important for me to be a part of the film, even though there was no acting role for me. Through the producing I got to take part in the film and see it through to the end. That’s the producer’s job: make sure things stay on the rails. It’s a really interesting side to film-making – we don’t have to be in front of the camera.”

He adds that he is working on several projects and “plans to tell some great stories” with Brad Grey, his partner in the film company Plan B. While he produces, Jolie is starring in a high-action thriller coincidentally called The Assassin, jumping off and on trains and training young assassins. “We have two boys at home who are very happy about it,” he says.

Pitt is clearly determined to explore the road less travelled and adds a coda about the future which may surprise his fans.

“I try not to do conventional action pictures or giddy romantic comedies nowadays,” he says. “I loved the Ocean’s films, which were all-day fun to make, but I prefer character roles. Nobody coaxes me to take my shirt off any more! I want to go and explore things, and if it’s new and interesting to me, then there’ll be others out there who’ll find it new and interesting too. Maybe not the masses, but there’ll be someone. The various times I’ve tried to satisfy other people, or some film industry ‘machine’, it has been miserable.”

Away from film, the Jolie/Pitt Foundation recently raised $1 million for relief in Darfur, and Pitt is now regularly pictured in magazines with his kids, playing and shopping. “I can’t recommend family life enough,” he says. “Astonishingly, I have become more efficient now that I have less time. Family comes first and so I have to work more quickly but somehow, even with sleep being nonexistent, paradoxically I get more work done.” At the Venice Film Festival Pitt said that he and Jolie wanted to have another child as soon as possible.

So, what does his own family think of it all now, I wonder.

He laughs. “One day I called my grandfather and asked how he was doing. He said: ‘We just saw your movie.’ I said: ‘Which one?’ And he called to my grandmother: ‘Betty, what was the name of that picture we were just watching?’ ” A celebrity enigma to us, but to his grandparents, he’s just their grandson.

Pitt shakes my hand courteously as we part, Jolie says a friendly goodbye, and together they head towards the flashbulbs.