The 2021 UEFA Super Cup was decided in on penalties as Chelsea lifted the trophy after the two sides played out a 1-1 draw after extra time in Belfast.
Ziyech opened the scoring, combining well with Kai Havertz to finish in the first half.
The Spanish side equalised in the second half through Gerard Moreno, who combined well with Boulaye Dia before finishing.
The Blues won the match 6-5 on penalties after a genius substitution by Thomas Tuchel, bringing on Kepa Arrizabalaga who saved two penalties.
The first chance fell to Timo Werner, who tested Sergio Asenjo but the Argentine was equal to the shot, punching it away to safety.
Chelsea opened the scoring 27 minutes in and it was the man in form Ziyech. Havertz pulled the ball back from wide on the left wing and Ziyech hit a left footed shot into the floor from 10 yards out to beat Asenjo in the Villarreal goal.
Villareal should have been level just after the half an hour mark as Dia burst through the middle of the pitch but luckily Edouard Mendy rushed off the line to deny the striker.
Alonso tested Asenjo with ten minutes utnil half time. Ziyech did well to beat his man on the wing before delivering a perfect ball into the box which Alonso turned goalwards but was denied by a fantastic save.
Ziyech finished the half in the worst possible way, being taken off after a nasty shoulder injury. The Moroccan was replaced by Christian Pulisic.
Villarreal should've been level going into the break as former Liverpool man Alberto Moreno smashed a left footed volley off the underside of the crossbar but luckily for the Blues it bounced infront of the goal line.
The Spaniards had another glorious chance in the second half and were once again denied by the woodwork as Mendy gifted the ball to Villarreal with a slip from a goal kick. Gerard Moreno broke before going one on one with Mendy but his shot was pushed onto the post by the Senegalese goalkeeper.
The Blues were on the backfoot for most of the second half, forcing Tuchel into a triple change on the 65th minute. Andreas Christensen, Mason Mount and Jorginho replaced Kurt Zouma, Werner and N'Golo Kante.
Villarreal were level with 20 minutes to go through Moreno. The Spanish international played a one-two with Dia before finishing into the roof of the net.
The game faded out with limited chances as the match headed into extra time.
Pulisic missed a guilt edge chance on the 100th minute as the ball fell to the American inside of the Villareal box, he does well to take the ball down but his shot towards goal just went past the post.
The second half of extra time saw Chelsea dominate again as Mount's shot was fantastically tipped wide by Asenjo to keep the scores level.
Tuchel used his final sub to bring on Kepa Arrizabalaga as the game headed to penalties.
Havertz stepped up for the first penalty and Asenjo saved it down to his left.
Moreno scored the first for Villarreal, smashing the ball off the right hand post on the way in to make it 0-1 to Villarreal.
Azpilicueta's strike beat Asenjo with power despite the goalkeeper diving the right way to make it 1-1.
Aissa Mandi's penalty was kept out as Kepa dived to his right to keep out the Villarreal man. It remained 1-1.
Alonso scored his penalty despite a slip to make it advantage Chelsea. 2-1.
Pervis Estupinan made it 2-2, sending Kepa the wrong way.
Mount scored to make it 3-2 to Chelsea.
Moi Gomez made it 3-3 despite Kepa getting a hand to it.
Jorginho took his trademark penalty, sending the goalkeeper the wrong way before stroking it home to make it 4-3.
Dani Raba converted to make it 4-4 as the shootout went into sudden death.
Pulisic converted from the spot to give an advantage to Chelsea, sending the goalkeeper the wrong way. 5-4.
Juan Foyth made it 5-5, putting it to Kepa's left as the goalkeeper dived the other way.
Antonio Rudiger stepped up for the sixth penalty, sliding it to the keeper's left as the goalkeeper was left standing. 6-5 to Chelsea.
Kepa denied Raul Albiol to win the Super Cup for Chelsea!