The Partenopei have rediscovered their form and are unbeaten in four games, while the visitors have struggled and are without a win in their three previous league outings.
Napoli's season looked to be on the verge of collapsing just two weeks ago when they were knocked out of the Coppa Italia at the semi-final stage by Lazio, following a five-game winless run in the league.
They will now face Dnipro Dnipropetrovsk in the semi-finals of that tournament and hopes are high that they can go all the way and end a barren run of 26 years without a European trophy.
It is quite some achievement for Napoli manager Rafael Benitez, who has reached a seventh European semi-final in the last 12 years and has guided Valencia and Chelsea to success in the competition.
Winning the Europa League may be their best way of getting back into the Champions League, as they are fourth in the Serie A table and are five points away from catching Roma and Lazio.
Recent form in Serie A: DLDLWW
Recent form (all competitions): LLWWWD
Napoli aren't the only team hoping to secure a place in the Champions League, as Sampdoria are right behind them in the table and have their own ambitions of breaking into the top three.
Sinisa Mihajlovic's side were in brilliant form last month and they won all four of their league fixtures in March to really put the pressure on the teams above them.
Things have not gone their way since they returned to action following the international break, and they have failed to win any of their previous three games.
The most frustrating of those came last weekend, when they were held to a goalless draw by struggling Cesena, despite having all of the possession and plenty of chances to claim the points.
It has left them in fifth place and by the time that they play on Sunday evening, they could slip even further down the table if Fiorentina are able to beat Cagliari in their clash at the Artemio Franchi.
Recent form: WWWLDD
Sampdoria will have just one absentee this weekend, as an injury has ruled Fabrizio Cacciatore out of contention.
Napoli possible starting lineup:
Andujar, Henrique, Albiol, Koulibaly, Strinic, Inler, Lopez, Callejon, Gabbiadini, Hamsik, Higuain
Sampdoria possible starting lineup:
Viviano, De Silvestri, Silvestre, Romagnoli, Regini, Soriano, Palombo, Obiang, Eder, Okaka, Eto'o
Head To Head
That result stretched Napoli's unbeaten run against Sampdoria to seven games, with five of those matches ending in wins for the Azzurri.
The Naples outfit are also scoring for fun at the moment and they have netted 12 goals in their last four outings, compared to just two for Sampdoria in their previous four games.
We say: Napoli 3-1 Sampdoria
Napoli have returned to form at the perfect time and they are on course for a memorable end to the season. They will be buoyed by recent results against Fiorentina and Wolfsburg and they should have enough quality to see off Sampdoria, which is why we are backing Benitez's men to claim the points.