Rafael Benitez's men saw off Wolfsburg in the quarter-finals to book their ticket for the last four, with Dnipro proving to be too strong for Club Brugge.
The Liga side, meanwhile, defeated Zenit 4-3 on aggregate in the last eight, whereas Fiorentina eliminated Dynamo Kyiv.
Sevilla are the defending champions following their win after penalties over Benfica last season, also having won the trophy in 2005-06 and 2006-07.
Fiorentina last made it to the final of the Europa League in 1989-90, when it was still named Uefa Cup, with Juventus beating the Artemio Franchi side 25 years ago.
Napoli previously enjoyed Europa League success in 1988-89, when Diego Maradona guided them past Stuttgart.
It's the first time in Dnipro's history that the Ukrainian side have made it to the semi-finals of the competition.
The first leg will be played on May 7, with the second leg scheduled for May 14.
The final will take place at the National Stadium in Warsaw on May 27.
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