The French defender, a half-time substitute in the 1-1 draw with FC Midtjylland, became the club's youngest ever player in the competition.
At 18 years and 25 days, he broke Antonio Barragan's record (18 years and 59 days) in Denmark, and conducted himself admirably after replacing Fabinho.
It was undoubtedly and incredible moment for the former Orleans player, who joined Jurgen Klopp's side in January 2019.
And it was completing the move in that transfer window which allowed him to have one of the best seats in the house on another historic night for Liverpool.
It may seem hard to believe but Koumetio was actually a ball boy at Anfield when they beat Barcelona 4-0 in the second leg of their Champions League semi-final in 2019.
A substitute appearance for Billy Koumetio. The youngest @LFC player ever to make his debut in the Champions League. He was a ball boy at Anfield the night that Liverpool beat Barça 4-0.
— Gary Lineker (@GaryLineker) December 9, 2020
He witnessed Trent Alexander-Arnold's corner taken quickly pitchside but against FC Midtjylland he was trying to get on the end of the set-pieces.
Recalling the night when interviewed by LiverpoolFC.com, he said: "It was [blows cheeks]… amazing, unbelievable. I could see the big boys, the big players, in front of me. It was a great experience for me.
"That drives me a lot. When I was sitting so close to the pitch and saw the big boys, they really inspired me.
"I was motivated to work really hard and [in order] to go to that level."
And while he appears destined to be a top centre-back, Koumetio has also admitted he was previously a left winger in his younger days but now has teammate Virgil van Dijk as an idol.
He revealed: "When I used to play for Lyon, I was playing left winger. Then I played left-back, too. I think it was Under-14s and at the end of the season the coach put me at centre-back - I think because of my height.
"Now I'm very happy because I think it's my position and it's better for me.
"I was trying to get my own style but at the moment Virgil van Dijk really inspires me. I go to the game most of the time and I like watching Virgil doing his game very, very well. Sometimes I'm trying to copy him."
The French youngster made his Champions League debut on the same night as Leighton Clarkson and their manager was full of praise for them.
"He (Koumetio) will learn and especially we let them have the experience without making this one game too big," said Jurgen Klopp.
"It is a wonderful thing to have your first Champions League game but your career is about how many you have.
"Both boys are already really skilled but they have a lot to learn and we will give them the time to do so.
"They helped us a lot because we could rest other players, which is very important.
"I am pretty sure it was a big night for both of them, I am really thankful they are as good as they are, that is the reason why we can use them, but I know there is more to come."
Liverpool defender Billy Koumetio made history on Wednesday night in the Champions League.