The home side have also enjoyed a strong recent run, registering three victories in all competitions to boost their chances in Serie A and the Coppa Italia.
After a number of less-than-convincing performances during his opening weeks as Barcelona boss, Quique Setien would have naturally had concerns that his stint at Camp Nou could become short-lived.
However, having recorded seven wins from nine games, the former Real Betis man has now settled into life at the Catalan giants and will be confident of eventually edging out Real Madrid for the La Liga title.
Having come through hard-fought contests with his ex-club and Getafe, Saturday's 5-0 demolition of Eibar came at the right time ahead of what should be a testing encounter in Naples.
Lionel Messi had gone four games without finding the back of the net before that contest, subsequently ending that drought with the latest four-goal haul of his historic career.
The Argentine will now want to take that form into Tuesday's meeting with Napoli after only scoring twice from five outings during the group stages.
The biggest concern for Setien ahead of this game will be Barcelona's away form, with defeats having been suffered at Valencia and Athletic Bilbao in recent weeks.
While they got back to winning ways on the road against Betis on February 9, the success only came courtesy of fighting back from early deficits at the Benito Villamarin Stadium.
Although Setien will want to keep more clean sheets on their travels in the long term, scoring at least one away goal will be the main target during the first leg in order to discourage a Napoli side who are seemingly on an upward trajectory.
The negative results led to Napoli dropping down into mid-table, a position once deemed unthinkable given the club's place towards the top of the table in recent years.
However, the former AC Milan chief has turned things around, guiding Napoli to six wins from seven matches, subsequently helping the club's cause in both domestic competitions.
Although Coppa Italia triumphs over Lazio and Juventus made the headlines, their work in Serie A has taken Gli Azzurri back into contention for next season's European places.
Several of their key men have chipped in with goals in recent matches, although three matches have passed since Napoli found the back of the net in the first half.
Nevertheless, Gattuso will not mind providing that his players continue their strong finishes to matches, something which may be required to keep Barcelona's away goals down to a minimum.
During the group stages, Napoli came through their games with Liverpool, Red Bull Salzburg and Genk conceding just the one goal, which came from the penalty spot.
While there has been a change in the dugout since those fixtures were played, Gattuso will want to see more of the same from his players, a resoluteness which will most likely be required against a team of Barcelona's quality.
Napoli Champions League form: WDWDDW
Napoli form (all competitions): WWLWWW
Barcelona Champions League form: DWWDWW
Barcelona form (all competitions): WWLWWWW
With having an extra day of preparation, Gattuso may opt to retain the same XI which began the win at Brescia on Friday night.
Napoli possible starting lineup:
Ospina; Lorenzo, Manolas, Maksimovic, Rui; Ruiz, Demme, Elmas; Politano, Mertens, Insigne
Barcelona possible starting lineup:
Ter Stegen; Semedo, Pique, Lenglet, Firpo; De Jong, Busquets, Arthur; Messi, Griezmann, Vidal
Head To Head
Tuesday night's fixture will represent the first time that these two clubs have faced each other in a competitive match.
We say: Napoli 1-2 Barcelona
Given Napoli's recent form, Barcelona should not have it all their own way on Tuesday evening. However, the visitors are starting to improve under Setien, and we feel that the Catalan outfit will return to Spain with a slender advantage.