The tie is delicately poised following a 1-1 draw in the first leg back in February, and the winner will advance to Lisbon for a knockout tournament to determine the winner of this season's European Cup.
Barca should be fired-up for Saturday's contest as they look to move on from the disappointment of the 2019-20 La Liga campaign, where they relinquished control of the La Liga title to bitter rivals Real Madrid.
The Catalan giants have had their problems this season but must still be taken extremely seriously in this competition, which resumes on Friday night following the coronavirus outbreak.
Barca are actually unbeaten in their last 35 Champions League matches on home soil, while they have not lost in any of their last 15 home fixtures against Italian opposition, picking up 12 victories in the process.
Five-time European champions, the team's last success in this competition came back in 2015, and they were incredibly eliminated by Liverpool in the semi-finals of last season's tournament despite running out 3-0 winners in the first leg of their last-four tie with the Merseyside giants.
Napoli also disappointed in their domestic league during the 2019-20 campaign, only finishing seventh in Serie A, some 16 points behind fourth-placed Lazio.
Gennaro Gattuso's side did beat Lazio 3-1 in their last league game of the season on August 1, though, and they could be sharper than Barca for this match, having only just finished their domestic campaign.
Napoli have actually never been past this stage of the Champions League, losing to Chelsea and Real Madrid in their last two last-16 ties. What's more, the Italian side have only won seven of their last 21 matches in this competition and have lost their last four two-legged ties against Spanish opposition.
Defeats on their last three visits to Spain, coupled with an overall away record of two wins and five defeats to La Liga opposition, means that the Italian outfit are the underdogs heading into Saturday's contest.
They are yet to lose in this season's Champions League, though, and impressively overcame the reigning champions Liverpool at home in the group stages of the competition before claiming a point at Anfield.
Barcelona Champions League form: WWDWWD
Barcelona form (all competitions): DWWWLW
Napoli Champions League form: DWDDWD
Napoli form (all competitions): DWLWLW
Ousmane Dembele trained with the first team on Wednesday as he continues his recovery from a long-term hamstring problem, although it seems unlikely that the Frenchman will be involved against Napoli, having spent an extended period on the sidelines with his latest issue.
Insigne picked up the issue against Lazio last weekend, and he trained individually on Wednesday as he fights to prove his fitness for the clash at Camp Nou.
Barcelona possible starting lineup:
Ter Stegen; Semedo, Pique, Lenglet, Alba; Roberto, Rakitic, De Jong; Messi, Suarez, Griezmann
Napoli possible starting lineup:
Ospina; Hysaj, Di Lorenzo, Koulibaly, Mario Rui; Ruiz, Demme, Zielinski; Callejon, Mertens, Insigne
We say: Barcelona 2-1 Napoli
Barca have had their problems this season, and we are expecting a very close game on Saturday night as Napoli certainly have the tools required to advance. It is difficult to look past Quique Setien's side at Camp Nou, though, and we fancy them to book their spot in the quarter-finals courtesy of a narrow win.