The pair engaged in some serious flirting on the Tonight Show with Jay Leno - to the point where it almost became uncomfortable to watch.
The actress even fed the comedian sweets from her cleavage, while he made ever more suggestive comments.
After Longoria plucked an M&M from her plunging bustier and handed it over, Brand said: "This one's melted a little bit from your cleavage. Could I have the bit that's still in there?"
Sweet talker: Eva offered new friend Russell an M&M from her bustier. He said he would prefer the bit that melted in her cleavage
Joker: Brand teases Tonight show host Jay Leno
Brand seems set to conquer America after starring in Forgetting Sarah Marshall and bagging a prime job presenting the MTV Awards with Britney Spears.
He spoke to Leno about meeting the Queen - crudely joking that he had wanted to fondle her breasts at the Royal Variety perfomance - and added that Leno fancied his mother, Barbara.
And when Eva suggested she had put on weight, he grinned and said: "You look all right to me, love."
The stars, both 33, appeared on The Tonight Show with Jay Leno.
Longoria laughed at the British comic's jokes and looked at him coyly over her shoulder, playing with her hair.
At one point they got off the sofa to stand opposite each other - with 6ft 1in Brand towering over Longoria, who is 5ft 2in.
He tried to shock Longoria, who is married to basketball star Tony Parker, by offering to pee on her - but she laughed.
He said: "If ever there comes a time when you want a bit of pee in your marriage, I'll give you my number."
Brand's attentions were not confined to Longoria - he was caught on camera taking a sneeky peek at singer Ingrid Michaelson's bottom.
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