Both teams started the afternoon winless in the league phase, and they showed real intent to change that with Domingos Quina and Nicolas Pepe firing over at either end within four minutes.
El Submarino Amarillo then cut through their hosts with two eye-catching passages of play in a matter of minutes, although Georges Mikautadze squandered a golden opportunity and Neofytos Michail rushed out to deny Pape Gueye.
Pafos shored things up defensively and there was a period where both teams moved the ball around nicely without causing any real problems.
Pepe had started to look frustrated at times with Ken Sema doing well in their personal battle, and the Villarreal winger was let down by a poor touch that allowed David Goldar to help Michail after a poor pass.
Santiago Mourino then blazed a strike harmlessly over the crossbar, and Ayoze Perez’s header was routinely saved, embodying the lack of conviction that had been shown throughout much of the first half.
The hosts wasted no time in the second period, going ahead in a UCL proper match for the first time in their history, as Luckassen rose dominantly to head in Sema’s corner. Quina then saw a shot from range saved with confidence flowing for Juan Carlos Carcedo’s side, while Gueye struck wildly off-target and Perez headed over at the other end.
Marcelino made all five of his substitutions in a five-minute period in an effort to get his side back in the game, and Tani Oluwaseyi saw a header saved shortly after his introduction. Pepe then flashed a shot marginally wide and a venomous Gueye shot was blocked as the hosts stood firm.
The visitors kept coming but Gerard Moreno headed wide and Santi Comesana’s speculative effort was saved, as Pafos recorded their third clean sheet in the league phase of the UCL this term to become the first Cypriot side since November 2011 to win at this stage of the competition.
They also inflicted a damaging loss for Villarreal, who have just one point from their four games and have failed to score in each of their defeats.
Flashscore Man of the Match: Derrick Luckassen (Pafos)