Ashton, 32, and Natalie, 29, star alongside each other in new flick No Strings Attached, in which they play a couple who try to have a sexual relationship without getting romantically attached.
But it seems their on-screen romance scenes aren't as glamorous as they appear.
Portman, who recently announced she was engaged to choreographer Benjamin Millepied and pregnant with their first child, told E!Online.com: 'It's awkward! It's always awkward.
'It's just weird to kiss someone that you wouldn't choose to kiss in your personal life.'
Although the Golden Globe winner admitted she just buckled down and got on with it.
She added: 'You get over it. You laugh through it and act like an immature kindergartner, which is what I did much of the time.'