Photos of Hollywood star couple Brad Pitt and Angelina Jolie appearing to have a tense exchange at a Sydney hotel last week have emerged.

Jolie, 39, who recently underwent a double mastectomy as a preventative measure against cancer, was pictured with a cigarette in-hand after the row, according to In Touch magazine.

"When Brad threw up his arms, you could see the frustration on his face," an eyewitness said of the nasty fight that took place on November 17 on a balcony at the Intercontinental Sydney hotel.

"He was clearly exasperated with her. They kept talking over each other and putting their hands up in anger. They were upset but getting nowhere. Angie looked like she was on the verge of tears," it added.

Pit apparently ended the bust-up by walking off leaving Jolie to finish her cigarette before they both headed to the premiere of the actress' new film 'Unbroken'.