Both sides' star striker was on target in Naples, where it ultimately ended 1-1 - setting up a titanic tussle in Catalonia.
Match preview
Forever linked by Diego Maradona, last month Barcelona and Napoli convened at the stadium that now bears his name, after both made it rather unconvincingly through the Champions League's autumn group phase.
Barca's Robert Lewandowski turned back the clock to produce a fine finish as the hour-mark approached - moving within seven goals of his century in Europe's top club competition - before the hosts' main marksman Victor Osimhen levelled matters on 75 minutes, in his first appearance since returning from the Africa Cup of Nations.
Though Lewandowski's 12th goal in as many Champions League knockout games was not quite enough to earn Xavi's men a valuable first-leg lead, they will be all-square ahead of this week's return game on home turf and remain unbeaten in five meetings with the Partenopei.
Knocking Napoli out of Europe for the third time in five years would see the Catalan club make a first quarter-final appearance since 2020 - and results since Xavi announced his forthcoming departure suggest they can progress again this season.
Following Friday's 1-0 win over Mallorca, secured by Lamine Yamal's superb second-half winner, Barcelona are unbeaten in eight matches and - despite sustaining a number of injuries - have kept clean sheets in each of the last three.
Still trailing behind old foes Real Madrid in La Liga's title race and also out of the Copa del Rey, Barca are surely relying on landing Europe's top prize if they are to avoid ending a difficult campaign without silverware.
When the Blaugrana have avoided defeat away from home in the first leg of a Champions League tie, they have then gone through on 20 out of 21 previous occasions. However, they have not won any of their last four knockout matches since beating Napoli in the 'Maradona derby' four years ago.
Napoli, meanwhile, are burdened by a history of failing to recover from first-leg setbacks in UEFA competition, having been eliminated the last 11 times they have failed to take a lead into an away leg.
Quarter-finalists last year, the Serie A champions have been unable to set the Champions League alight this term, as Rudi Garcia and Walter Mazzarri both failed to adequately replace Scudetto-winning coach Luciano Spalletti, and they stumbled through as Group C runners-up.
Interim boss Francesco Calzona returned to Naples just days before last month's first leg, becoming the club's third head coach of the season, but with Osimhen back from international duty and Khvicha Kvaratskhelia finally finding his top gear, the picture has begun to brighten.
Though still in danger of missing out on European qualification, Napoli are unbeaten in five matches since Calzona took the reins, and between draws with Cagliari and Torino they demolished struggling Sassuolo 6-1 and edged out ailing Juventus at Stadio Maradona.
Osimhen has scored five goals during that spell, while 'Kvaradona' struck four times - including the opener against Torino on Friday - so the Italian champions are not without hope as they head from Campania to Catalonia.
Napoli have also won five of their eight Champions League away games since the start of last season - as many as in the previous 21 - and should not be underestimated, despite missing the spark that made Spalletti's side so special.
Barcelona Champions League form:
W
W
L
W
L
D
Barcelona form (all competitions):
D
W
D
W
D
W
Napoli Champions League form:
L
W
D
L
W
D
Napoli form (all competitions):
D
D
D
W
W
D
Team News
Since February's first leg, Barcelona's injury woes have developed into something of a crisis, as Frenkie De Jong (ankle) and Pedri (hamstring) will both be absent from the hosts' starting XI on Tuesday evening.
ACL-victim Gavi is already unavailable, so Andreas Christensen and Ilkay Gundogan may be joined by Fermin Lopez in a makeshift midfield; Ferran Torres, Alejandro Balde and Marcos Alonso are still sidelined too. Raphinha's presence is also in doubt, due to an ankle problem, but Ronald Araujo returns from suspension.
In Naples, 16-year-old Lamine Yamal became the youngest player to appear in a Champions League knockout game, and he will now aim to be the youngest goalscorer in the competition's history. More than twice his teammate's tender age, Robert Lewandowski starts up front for the Blaugrana, having racked up 18 goal involvements from his last 12 appearances in the latter stages.
Meanwhile, Victor Osimhen's equaliser against Barca was his ninth Champions League goal, and one more would make him the most prolific Nigerian player in the competition, moving clear of Obafemi Martins. Last season's Capcannoniere should lead a front three also featuring Khvicha Kvaratskhelia and Matteo Politano.
Jens Cajuste and Cyril Ngonge may miss out with thigh injuries, while centre-back Amir Rrahmani limped off against Juventus with a similar issue and was an unused substitute on Friday night. Leo Ostigard stands ready to deputise for the latter if required.
In midfield, Piotr Zielinski must be replaced, as he was not registered for this phase of the competition after refusing to sign a new contract - the Poland international is expected to join Inter Milan this summer.
Barcelona possible starting lineup:
Ter Stegen; Kounde, Araujo, Martinez, Cancelo; Gundogan, Christensen, Lopez; Yamal, Lewandowski, Felix
Napoli possible starting lineup:
Meret; Di Lorenzo, Ostigard, Jesus, Olivera; Anguissa, Lobotka, Traore; Politano, Osimhen, Kvaratskhelia
We say: Barcelona 2-1 Napoli (Barcelona win 3-2 on aggregate)
Not only have they put together a more consistent run of results - and should really have won the first leg - but Barcelona have done so in the face of adversity, with several squad members missing through injury.