And it wasn't the fact the Irishman flashed a smile.
Humphries, the defending world champion in darts, had the honour of being the latest guest on The Overlap podcast.
"Had a great time filming for @WeAreTheOverlap today, with some of the best footballers to have played the game," Humphries posted on X.
Humphries, a passionate Leeds United fan who was named Luke by his father in a tribute to the club, added it 'was a great laugh and enjoyed the experience'.
The darts sensation also shared a number of snaps from his day filming the show.
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Humphries was pictured with Ian Wright, Jill Scott, Gary Neville, Paul Scholes and Keane.
Although Humphries wore his blue darts shirt, Wright, Scott, Neville, Scholes and Keane all dressed in Christmas sweaters for the occasion.
Scholes and Neville were decked in out in Manchester United-themed sweaters while Scott and Wright wore designs based on previous clubs Manchester City and Arsenal kits respectively.
As for Keane, he had perhaps the most eyebrow-raising outfit of the lot as the Irishman opted for a Tottenham Hotspur sweater.
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Given Keane's 12-year association with Manchester United, where he won seven Premier League titles, four FA Cups and a Champions League trophy, seeing him in a Tottenham-themed sweater was perhaps a surprising sight.
However, Keane has previously revealed the north London club is who he supports.
"I am a Spurs fan, I played for Man United but Spurs are my team," Keane said on the Stick To Football podcast in December 2023.
The 67-time Ireland international also spoke about his support for Tottenham at an event for children's cancer charity Barretstown in 2015.
"Just because I played for Manchester United didn't mean I was a fan of the team," Keane said.
"When I played for Rockmount, one of my teammate's fathers used to bring me to training and he supported Tottenham.
"That's where it started, I liked their players, the likes of Glenn Hoddle and Clive Allen.
"But after I'd come back from trial at Nottingham Forest, Spurs offered me a trial.
"I turned it down because Forest had been good me, I liked the club and felt some loyalty to them. I had a soft spot for Spurs, and still do."
Humphries' appearance on The Overlap comes with less than four weeks to go until the 2024/25 World Championship.
The world No. 1 will look to defend his crown but faces stiff resistance from the rest of the field, with Luke Littler entering the tournament on the back of his first ranked televised win at the Grand Slam of Darts.
It was Humphries who beat Littler in an enthralling World Championship final last January, but the 17-year-old will no doubt want to go one better with the tournament beginning on December 15.