The Arsenal captain produced a moment of brilliance 15 minutes from time, curling a powerful effort into the bottom corner off the post to settle a match his side had dominated without making their chances count.
It was a fittingly dramatic ending to a frustrating night in Naples, where Arsenal repeatedly threatened but struggled to produce the finishing touch until Odegaard finally stepped up.
Arsenal waste chances in Naples
Mikel Arteta’s side controlled much of the opening half but were badly let down by their finishing.
Bukayo Saka, Eberechi Eze and Mikel Merino all had opportunities as Arsenal looked dangerous from both flanks, while Napoli goalkeeper Alex Meret made an important save to deny Merino’s diving header.
The visitors finished the first half with 13 attempts, but too many were either weakly struck or sent high over the crossbar.
Saka had perhaps the clearest opportunity when he fired wildly over from inside the box, while Declan Rice also sent an effort onto the running track surrounding the pitch.
Napoli remained dangerous on the counter and Kevin De Bruyne, now 35, showed glimpses of his quality against his former Premier League rivals.
The Belgian forced David Raya into a save with a powerful effort from distance, but Arsenal otherwise managed to limit Napoli’s threat.
Odegaard finally breaks Napoli resistance
Napoli were forced to replace Meret at half-time, but the change did little to alter the pattern of the match.
Arsenal continued to create chances but waste them.
Hincapie missed a particularly good opportunity early in the second half after Ben White’s header left the goal open from close range.
Arteta turned to his bench with 25 minutes remaining, introducing Bruno Guimaraes and Christos Tzolis in an attempt to find the breakthrough.
The frustration continued until Arsenal’s captain took matters into his own hands.
Odegaard collected the ball outside the penalty area and produced a superb finish that flew into the bottom corner via the post, finally giving Arsenal the reward their dominance had threatened to produce.
The goal was the Norwegian’s fourth of the season and provided a timely reminder of his ability to produce decisive moments.
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