SSC Napoli 0-0 Villarreal CF
The Serie A high-fliers' hopes of building a first-leg lead amounted to nothing, Salvatore Aronica's late dismissal compounding their misery.
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SSC Napoli and Villarreal CF will meet again on 24 February on even terms after sharing a goalless draw.
There was little to choose between the two sides in a cautious UEFA Europa League round of 32 encounter which was only occasionally enlightened by the skilful Ezequiel Lavezzi, who came closest to scoring in the second half.
Having struck just twice in their last four European home matches the result will have come as little surprise to the Naples crowd. Other than Hugo Campagnaro's long-range effort on 14 minutes, and a presentable chance at the other end for Nilmar moments later, when the Brazilian scuffed his shot after being played through by Giuseppe Rossi, the two sides struggled to create openings before the interval.
It was an intriguing clash of styles, nonetheless, Andrea Dossena and Christian Maggio frequently spraying long, diagonal balls to the opposite flank in the hope of servicing Edinson Cavani, while the visitors adopted a more intricate passing style. The Partenopei did occasionally try a different ploy, the impressive Lavezzi twice playing in Cavani with cunning passes straight through the heart of Villarreal's defence.
Proceedings picked up after 70 minutes when a wonderful quick passing move involving Nilmar and Rossi gave Borja Valero a chance which he blazed wide. It spurred Walter Mazzarri's men to life. Another attack ensued, Lavezzi haring on to Maggio's searching pass but though he beat the advancing Diego López, his lob landed on top of the net.
With a minute remaining, Villarreal threatened briefly, Valero warming Morgan De Sanctis's palms with a fierce shot, before Salvatore Aronica earned his second yellow card of the evening for a foul on Nilmar which will rule the defender out of the return leg in Spain.