The 40-year-old TV presenter was left shocked on 'The Tonight Show Starring Jimmy Fallon' on Tuesday night (06.01.15) when the actress - who has daughters Sunday, six, and four-year-old Faith with husband Keith Urban - recalled a story of when she fancied him and managed to get an invite to his flat, but was ultimately left disappointed.
While Jimmy - who also has two children with his wife Nancy Juvonen - was halfway through recounting his side of events he admitted he couldn't remember exactly where he was working at the time and Nicole then interjected by saying: "I just remember I liked you."
She then assured Jimmy "not now, I'm married now," and returned to the story by adding: "Not in that way," amid laughter and cheering from the studio audience.
A stunned Jimmy then said: "Wait ... what? Wait, what?"
Nicole struggled to reply as she was laughing so much before saying: "So, Rick, our mutual friend said Jimmy wants to meet you, you can go over to his apartment. I was single so I'm like, 'OK, yeah cool.' "
Jimmy said: "Wait. What? What are you talking about? Did I date Nicole Kidman? Did we go on a date?"
She added: "So I go along and you're there in a baseball cap and, like, nothing. And you didn't talk, you wouldn't say anything. You were like, 'Hey, um, um, um.' And I'm like, 'OK, so...'
"And then you put a video game on or something, and I'm like 'This is so bad.' "
Jimmy then collapsed off his chair in hysterics, unable to believe he had blown his chance with Nicole, while she couldn't stop laughing and turned to the audience and added: "It was bad!"
She continued: "I swear after about an hour and a half you didn't talk at all so I thought, 'He has no interest, this is embarrassing.' I kinda left and went, 'OK, no chemistry. Or maybe he's gay?'
Jimmy said: "Oh my God, I had no clue.
"I'm in shock right now. I can't believe I dated Nicole Kidman. This is unbelievable.
"But wow did you make a good decision. You made a fantastic decision. Keith Urban is so much cooler than I am."
And he couldn't resist a final joke about the "very embarrassing" situation, adding: "But he's always on tour ... I'm not always on tour."
Earlier in the show Jimmy started explaining his version of the story in which he revealed a mutual friend of the pair called Rick had phoned him up and told him to go and buy some cheese and crackers because he was bringing Nicole round to his apartment in 10 minutes.
He added: "I'm like, 'Cheese and crackers? I don't have dinner parties, I have video games and sneakers.'
"He said to get brie and I didn't even know what that was."