And the Spaniard will be all too aware of the pressures that come with contesting a final in this competition, having won it with Chelsea last season.
The Serie A outfit come into this clash one down in the tie after Jackson Martinez scored the only goal in the opening leg in Portugal last week.
Napoli had been on a run of eight games unbeaten in the build-up to that encounter, but returned to winning ways domestically on Sunday with a 1-0 victory at Torino.
Porto, meanwhile, are adjusting to life under interim head coach Luis Castro, who tasted defeat for the first time at the weekend with the side's fifth league loss of the season at Sporting Lisbon.
The only previous meeting between these sides in European competition came back in 1974-75, when the Italians won 1-0 in each leg in the UEFA Cup.
The men from Stadio San Paolo have hosted Portuguese opposition on four previous occasions and are yet to sample defeat, while Porto have lost eight times on their 13 previous visits to Italy.
Benitez, who is bidding to become the first manager to win the trophy in successive seasons with different clubs, has expressed concern about his side's congested schedule.
"It is certainly not easy to rest as they should when playing this high rate of games," he said. "We played two or three games in a few weeks and that has a cost.
"But we need to recover as quickly as possible and try to be bright on Thursday in the match against Porto to stay part of this European competition.
"For us it is like a final, a real final and we have to make the most of our chances."
Juan Camilo Zuniga (knee) and Rafael Cabral (knee) remain sidelined for Napoli, while Christian Maggio was reportedly hospitalised with a collapsed lung shortly after returning from the first leg.
Goalkeeper Helton (Achilles) is missing for Porto, while Alex Sandro serves a suspension having surpassed the yellow-card limit.
