It's hard to tell from the blurry screenshot above, but I was able to verify that Angelina is wearing the wrap shown below, just in black. Her exact wrap is $168 and you can click the image below to view or purchase. At the moment, it's only available in gray online but you might find it in black at your local store.
Ann Taylor has been featuring some pretty high-profile stars in their recent ad campaigns, including Heidi Klum, Katie Holmes and most recently Demi Moore. Think Angelina is next? She's still so unbelievably popular that I think it would be amazing for their brand. Just speculating.