The couple, who had a tumultuous beginning to their relationship, were together for just over ten years before calling it quits.
After meeting on the set of Mr and Mrs Smith the couple didn't work together again until the 2015 film, By The Sea, centered around a marriage crisis, written and directed by Jolie.
Talking to The Hollywood Reporter podcast, Awards Chatter, Jolie shared: 'We had met working together and we worked together well.
'I wanted us to do some serious work together...I thought it would be a good way for us to communicate.'
However, according to the 42-year-old actress working on the film with Pitt didn't necessarily help the communication between the two.
'In some ways it was, and in some ways we learned some things,' she explained. 'But there was a heaviness probably during that situation that carried on and it wasn't because of the film.
'It was something that we were dealing [with]...things happen for different reasons, and things...why did I write that exact piece? Why did we feel that way when we made it? I'm not sure.'
Jolie further added, 'A piece of art can be something that’s healing or something that’s difficult. I don't know. I'm glad we did that film because we did explore something together. Whatever it was maybe it didn't solve certain things, but we did communicate something that needed to be communicated to each other.'
Jolie further elaborates on their decade long relationship, explaining there were other 'life' factors that contributed to their failed marriage.
She says, 'Over the span of that decade, I did lose my mother, I did have my mastectomy, and I did then have an ovarian cancer scare and have that surgery as well, and other things of course that happened in life that you go through.'
Ending the interview, Jolie reflected on her mental state now.
'I don't enjoy being single. It's not something I wanted. There are no upsides, there's nothing nice about it. It's just hard.'
The couple share six children together - Maddox, Pax, Zahara, Shiloh, Knox, and Vivienne.