Mortimer, who has starred opposite Caine in Harry Brown and Cars 2, told Metro that he would have made an excellent 007.
Asked if their previous collaboration made up for not working closely on the new Pixar animation, the actress said: "Absolutely. I was in the fortunate position of having done an action movie with him.
"I'd have been really p*ssed off if I'd done a whole movie with the guy and hadn't met him."
Mortimer added of Caine's title character in Harry Brown: "He's dying of emphysema, between taking people out with AK-47s. He'd have been such a good James Bond."
Mortimer last year claimed that Caine was a "terrible giggler" on set, as well as being the "the most expert professional dude" she has ever worked with.
Watch the Cars 2 trailer below: