She had, you imagine, been planning her outfit for months. In the end, she chose a deliciously elegant Valentino gown, accessorised with Bulgari white gold and diamond jewellery. The effect was simply stunning.
But although she appeared composed as she took to the stage, inside she must have been shaking with nerves.
Yes, any woman who has had to come face to face with their ex and the woman who replaced her must surely have felt for Jennifer Aniston at the Oscars. It can't be easy to see the man you once thought loved you - and this is, after all, Brad Pitt we're talking about - in the company of a more beautiful, more famous and let's be honest, more talented A-lister. Let alone one he's fathered and adopted children with.
But that, surely, is the point. It's been four years since Brad and Jen split up. Four years. In that time, he's set up home with Angelina, embarked on raising a family with her, and still found time to make some great movies, earning an Oscar nomination.
Jen - well, she's dated Vince Vaughn. And Paul Sculfor. And John Mayer. And made The Break-Up, and He's Just Not That Into You. And given an interview where she declared Angelina's behaviour to be 'uncool'.
There's a wonderful line in When Harry Met Sally when Meg Ryan's character discovers her commitment-phobic ex has got engaged. 'All this time, I thought he didn't want to get married,' she sobs. 'But the truth is, he didn't want to marry me.'
Goddess-like though she is, it's unlikely Angelina bewitched Brad. He simply fell in love with her and decided she was the woman he wanted to start a family with.
If reports are to believed, Jen - now 40 - is planning to announce her engagement to John Mayer shortly. For her sake, I do hope that's true. If not, then maybe her next movie should be called Get Over It.