The Yellow Submarine have never won the competition, or even reached the final before, reaching the semi-finals just once in 2014-15, losing 6-2 to eventual winners Barcelona over two legs.
After two years of incredible European runs, the Copa Del Rey could prove to be an opportunity at more cup glory, but it will not be an easy route to the final.
The tie will be played between Tuesday 17th and Thursday 19th January at the newly renovated Estadio de la Ceramica, in a single knockout round which could potentially go to extra time and penalties.
Villarreal face Real Madrid today at the same venue in La Liga, which could give an insight into how the cup tie could play out.
The European Champions will also have the Club World Cup coming up in February and may be inclined to rest some of their biggest stars.
Villarreal only reached the third round last season, disappointingly losing to Sporting Gijon at home, and last reached the quarter-finals in 2021, before losing to Levante.
Real Madrid have not won the cup since 2014, when Gareth Bale scored a famous solo goal against Barcelona at Mestalla, but have failed to even reach a final since, coming closest in 2018-19 when they lost to Barcelona in the semi-finals.
The draw in full:
AD Ceuta FC vs Barcelona
Levante vs Atletico Madrid
Sporting Gijon vs Valencia
Deportivo Alaves vs Sevilla
Real Betis vs Osasuna
Villarreal vs Real Madrid
Real Sociedad vs Mallorca
Athletic Club vs Espanyol