Rafael Benitez's charges progressed to the last 16 of the UEFA Europa League with victory against the men from south Wales, but will be keen to get back to winning ways in Serie A after being held to a 1-1 home draw by Genoa last time out in the league.
And the Stadio San Paolo outfit could not have asked for a much kinder fixture on their return to the Italian top flight.
Livorno - currently 18th and one point adrift of safety - have struggled to make home advantage count this season.
Domenico Di Carlo's men have recorded just three victories at Stadio Armando Picchi this term, two of which came against the only teams that currently sit below them in the league.
Fourteenth-placed Atalanta are the highest-ranked team Livorno have beaten home or away this campaign, and Napoli's opponents this week have suffered four defeats in their last five matches on home soil.
Those figures should make Napoli confident of claiming victory, as should their record of having beaten Livorno in the last five meetings between the sides with a 12-2 goal difference.
Napoli made the best of their attacking depth in the reverse fixture back in October as Goran Pandev, Gokhan Inler, Jose Callejon and Marek Hamsik found the net in a 4-0 triumph.
Victory this time around would aid their quest to keep pace with top two Juventus and Roma, and Napoli midfielder Dries Mertens knows the importance of an early goal on Sunday.
"Sunday will be important to score a goal right away," he told Radio Kiss Kiss. " In short, it will be important not to repeat the mistakes made with Genoa. We must stay alert and focused for the full 90 minutes."
Napoli will be without the suspended Gonzalo Higuain and Raul Albiol for the trip to Livorno, while goalkeeper Rafael is set for a lengthy spell on the sidelines after surgery on a knee problem.
Livorno's struggle against the drop was made all the more difficult a fortnight ago when captain Andrea Luci was ruled out for the rest of the season with an anterior cruciate ligament injury.
