Villarreal saw off Dinamo Zagreb with a 3-1 aggregate win to set up a Europa League semi-final against boss Unai Emery's former side Arsenal.
Emery, who won the competition three times when in charge of Sevilla, took Arsenal to the final in 2018-19 when they were beaten by Chelsea in Baku.
His side held a 1-0 lead from the first leg over Dinamo Zagreb and took control of the return in the first half.
Paco Alcacer and Gerard Moreno both scored for the hosts before the break.
Mislav Orsic pulled one back for the visitors with 16 minutes to go.
But the Spanish side were able to see the game out to set up a semi-final against Arsenal, with the first leg taking place on 29 April.
"First of all, I'm used to meeting ex-teams so playing Arsenal, where I coached, is nothing new as an experience," said Emery.
"We'll face up to it with humility, pride and responsibility. This is a chance to establish Villarreal on the top rung of European football.
"This is Villarreal's fifth semi-final in Europe and, personally as a coach, it'll be my sixth across Sevilla, Arsenal, Valencia and now here. It shows we are capable, it makes us proud but I re-emphasise that we have to 'feel' the experience. We really need to go out and enjoy it."