And the 29-year-old made an almost immediate impact by scoring to help Aston Villa beat Club Brugge 3-1 in their last-16 first leg tie in Belgium on Tuesday evening.
Surprisingly left on the bench by Unai Emery, Asensio was brought on in the 64th minute with the Villans drawing 1-1 at the Jan Breydel Stadium.
An own goal from Brandon Mechele in 82nd minute put the visitors back into the lead after Maxim De Cuyper cancelled out Leon Bailey's early opener.
And in the 88th minute, Asensio sealed victory for Villa by firing in a penalty into the bottom left corner in what is his fifth goal for the club.
His appearance off the bench saw him create European Cup history by being the first player to reach a half-century of outings in the competition from the bench.
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It is his first appearance for Villa in Europe's premier competition since joining the club on loan from Paris Saint-Germain in February.
In total, the Spaniard has now featured in 70 Champions League matches.
That means he has only started 20 times in the tournament since his debut during the 2016/17 season.
He ended up winning the competition that campaign - scoring in the final as Real Madrid beat Juventus 4-1 in Cardiff.
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But as was often the case during his time at Los Blancos, his appearance at the Principality Stadium came from the bench.
In fact, from his 59 Champions League matches for Real, he was named amongst the substitutes on 42 occasions.
Though despite his lack of starts, he did lift the trophy three times - featuring in the 2017 and 2018 finals.
Moving to PSG in 2023, and his Champions League game time didn't improve.
From his ten appearances for Les Parisiens in Europe, he was named in Luis Enrique's starting XI in just three fixtures.
And he will be hoping it's not a similar theme at VIlla with the playmaker hoping to start in his side's second leg clash in the Midlands next week.
Since he linked up with Villa in the winter transfer window, Asensio has proven to be an instant fan favourite.
He has now found the back of the net on five occasions from seven matches in all competitions.
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Asensio previously scored twice in the comeback 2-1 victory over Chelsea last month.
He then followed that up with another brace in the 2-0 FA Cup fifth round win against Cardiff last weekend.