What we did know from various titbits they gave away in interviews, was that they weren't exactly BFFs.
But that could all be about to change after Brad extended an olive branch to Jen when he called her to congratulate her on her engagement to Justin Theroux.
According to The Mirror, during the call Brad even asked if he should expect an invite to the wedding.
“He jokingly asked if he should ‘save the date’, and they both laughed, but told her in all seriousness that he was really happy for her and Justin.
"He wished her luck and told her he hopes they’re very happy together."
The insider added: “Brad and Angelina are due to marry in the next few weeks and she wished him all the best for his wedding, too.”
Meanwhile more details of Justin's proposal have emerged.
He is said to have popped the question to Jen at Blue Hill restaurant in Greenwich Village, New York City during a meal to celebrate his 41st birthday.
A source also spilled all on the eight carat sparkler he presented the former Friends star with.
"It's a huge emerald-cut diamond. It's a rectangle with tapered diamond baguettes on the sides. It's beautiful," they told Life & Style magazine.
"Just after Jen got engaged, she called all her friends and told them about it. She was so happy and said she loves the ring. I think she was overwhelmed and overjoyed by the size and beauty of it!"
A spokesperson confirmed their engagement on Sunday in a short statement, which read: "Justin Theroux had an amazing birthday on Friday, receiving an extraordinary gift when his girlfriend, Jennifer Aniston, accepted his proposal of marriage."
> IN PICS: JEN'S STYLE EVOLUTION
Jennifer Aniston wears a white t-shirt, black blazer and flat cap on backwards.
Jennifer Aniston wears a full length figure hugging dress.
Actress Jennifer Aniston wears a gown with detailed top for the Emmy Awards.
US actress Jennifer Aniston arrives at the premiere of <em>Snatch</em> wearing a khaki green scarf and white t-shirt with a brown leather jacket and jeans.
Actress Jennifer Aniston arrives with then husband Brad Pitt at the Golden Globe Awards. She wore a blazer jacket with short necklace.
Jennifer Aniston wore a pink embellished gown at the Emmy Awards.
Brad Pitt and Jennifer Aniston at the premiere of <em>The Bourne Identity</em>. She wears a loose navy top.
Actress Jennifer Aniston wears casual cargo trousers with a navy vest.
Actress Jennifer Aniston wears a floral dress over black trousers.
Jennifer Aniston wears a floor-length dress with cut-out detail.
Actress Jennifer Aniston wears a strapless cream dress with embellished detail.
Actress Jennifer Aniston wears a simple black dress.
Actress Jennifer Aniston wears a cream dress.
Jennifer Aniston launches her debut fragrance wearing a short strapless cream dress.
Actress Jennifer Aniston wears a printed dress with black tights and shoes.
Actress Jennifer Aniston arrives at the premiere of <em>Wanderlust</em> wearing a fitted dress.
Jennifer Aniston wears a floral dress on the Hollywood Walk Of Fame.