Clooney appeared on the talk show on Thursday to discuss his new film, Tender Bar, but received an expected guest in the form of the Pretty Woman star.
During the interview the father-of-two's co-star in the romantic comedy Ticket To Paradise was seen scooting over to Clooney in her chair with a seemingly intentional sombre face, while wearing a pair of dark sunglasses.
Expressing that he was in complete shock, host Kimmel said: 'Oh my goodness, wow. Holy moly.
'George, I don't know if you're aware of this, but there's a woman sitting next to you.'
Meanwhile, the 60-year-old actor - who plays Roberts' husband in their latest film, but in real life is married to 43-year-old barrister Amal Clooney - echoed his co-star's blank expression, as if he had no idea what Kimmel was talking about.
Following the multi-Oscar winning actor's lack of expression, Kimmel said: 'Maybe I hallucinated that. It looked like Julia Roberts though.'
Clooney's 10-year-old co-star in his latest film, Daniel Ranieri, was also talking on the show, and after Roberts' appearance, Kimmel said: 'Hey, Daniel, have you ever seen Pretty Woman?'
Ranieri innocently replied: 'No.'
'Oh, you're gonna love it,' Kimmel responded.
Fellow Oscar winner Roberts has worked with Clooney on several occasions over the years, such as in films like Money Monster, Ocean's Eleven and August: Osage County.
Their latest film depicts a divorced couple who travel to Bali together to stop their daughter repeating their mistakes from 25 years ago, as reported by Deadline.
Roberts, who's married to cinematographer Daniel Moder - with whom she shares three teenage children, twins Hazel and Phinnaeus, 17, as well as Henry, 14 - has had many successes since starring in the 1990 romcom Pretty Woman, aged 23.
Her accolades include an Oscar for Best Actress in the 2000 film Erin Brockovich, which explores the story of a struggling single mother who becomes a legal assistant and challenges corporate pollution. The actor also earned an Oscar for her supporting role in Steel Magnolias.
Speaking of her marriage with Oprah for Harper's Bazaar in 2018, Roberts said: 'I’m so proud of my marriage. We just celebrated being married for 16 years this Fourth of July, and there’s so much happiness wrapped up in what we’ve found together.'
At the time Oprah asked the actor about how she copes with tabloid news when it comes to her kids.
Roberts responded: 'Sometimes we are in the grocery store and I won’t even know something is out, but we’ll see a tabloid and we’ll all be standing there like, "Oh, that’s uncomfortable. This is really uncomfortable."'
'What I like is when they write, “the $150 million divorce,” and then a week later a different tabloid says, “the $275 million divorce.” I’m like, “Well, somebody got a paycheck in the last week. This is getting good.”'
Roberts, whose other romantic films include Runaway Bride, Notting Hill and My Best Friend’s Wedding, also told The Times, in the same year, that following her marriage and the birth of her three children, she found reasons not to work and felt she had less to prove.
She also said to the news outlet: 'The mystique of movie stars? I think it’s long gone. I mean, what are you going to take away from meeting me?'
Well, judging by the reaction she just got when gatecrashing Clooney's interview, seemingly those who meet her will take away a lot.
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