The Paris Saint-Germain winger will face the Reds for just the second time in his career on Wednesday night.
Liverpool travel to the French capital for the first leg of their Champions League last 16 tie.
It will be Dembele's first meeting with the Premier League leaders since the semi-finals six years ago.
Then a Barcelona player, the forward came off the bench for the final three minutes of stoppage time.
However, he was still involved in what proved to be a crucial moment in the tie during his brief cameo.
READ MORE FOOTBALL NEWS
Cunha move in danger, Spurs lead race for talented teenager, Liverpool want star full-back
Bayern set to reject Kane request by snubbing 'really good friend' this summer
With Barca 3-0 up at the Nou Camp, Dembele led a counter-attack following a Liverpool corner.
After driving forward from his own half, he played a one-two with Lionel Messi on the edge of the opposition penalty area.
Despite having the goal gaping in front of him, though, the France international scuffed his effort straight into the hands of Alisson.
It was the last kick of the game and co-commentator Steve McManaman exclaimed 'what a miss'.
Most read in Champions League
Who could Arsenal face in Champions League quarter-finals?
Nwaneri could emulate Bellingham as Arsenal eye advantage in Champions League last 16
Atletico Madrid's secret weapons that make them huge Champions League contenders
Liverpool eye Champions League quarter-finals but face tough task against in-form PSG
Messi knew it, too as he dropped to his knees in agony as the hosts squandered the opportunity for a four-goal first leg lead.
Dembele's miss did prove costly a week later as Liverpool pulled off a miraculous comeback at Anfield.
Divock Origi and Georginio Wijnaldum both scored twice to secure a 4-0 victory and progression to the final, which they would go on to win.
Had Dembele scored his chance, the tie would have ended 4-4 on aggregate and gone to extra-time.
The Barca man had missed the second leg through injury as his woes continued to plague his time in Spain.
After signing from Borussia Dortmund in 2017 for £97million, Dembele scored 32 goals and provided 18 assists in 75 appearances for the Blaugrana.
However, he would miss a total of 141 matches for club and country during his six years with the LaLiga giants.
Despite winning seven trophies, including three league titles, Dembele was sold to PSG in 2023 for just over £40million.
Liverpool fans fear Mo Salah is saying goodbye in new bombshell interview with TNT Sports
Over a year-and-a-half on, the 27-year-old is having the best season of his career under Luis Enrique.
Dembele has scored 26 goals and added six assists in 33 matches across all competitions, with six of those strikes coming in Europe.
He also sent a warning to Liverpool ahead of their last 16 clash this week.
Speaking after PSG's win over Lille on Saturday, Dembele told DAZN: "We played a very good game today. We are preparing well for what is to come (Liverpool).
"Since the beginning of the season, (Luis Enrique) has been telling us to play good football.
"Everyone is participating, whether it's the midfielders, defenders or attackers. Everyone wants to be decisive.
"We are in a very good dynamic, we will try to keep it as long as possible. We are having a blast. Everyone attacks, everyone defends.
"We are a very united team that gives results like that. It's just fun for 90-95 minutes."
The former Rennes man added: "We know it's going to be a tough match. It's the Champions League. Liverpool finished first, they're also confident. It's going to be a great show."
Read More on talkSPORT
WWE fans call for star's signature move to be banned after brutal injuries revealed
Ex-Masters winner who went to prison set to end six-year Augusta National exile
PSG will travel to Anfield next Tuesday for their second leg against Liverpool as they battle for a place in the quarter-finals.
The winner will face either Club Brugge or Aston Villa in the last eight next month.