The Friends actress will be a presenter at the show and Pitt, 46, decided not to attend the awards even though his film Inglourious Basterds is a contender at the ceremony, reported US magazine.
Aniston, 40, who is single after splitting from singer John Mayer, had infamously run into her ex-husband during last year’s Oscars.
Oscar telecasters panned to Brad and Angelina, nicknamed Brangelina by the tabloids, as a visibly nervous Aniston walked on stage and the couple looked on with bemused half-grins as she stuttered on stage.
Pitt and the Along Came Polly actress announced their split five years ago in January 2004, and the actor soon stepped out with his Mr and Mrs Smith co-star Jolie.
Since splitting Aniston has been linked to a number of men including actors Vince Vaughn, Gerard Butler and Bradley Cooper while Brangelina are now bringing up a family of six children.