With the game in Belfast finishing 1-1 after extra-time, goalkeeper Kepa was brought on in place of Eduoard Mendy for the shootout.
The save against Albiol saw the shootout end 6-5 in Chelsea’s favor, handing Tuchel his second piece of silverware as Chelsea boss after last season’s Champions League final victory against Manchester City.
“Edou did a fantastic job before, it was a tough, tough game against a very difficult team. We won and we are so happy. All the team did a fantastic job and we have the medal.”
Hakim Ziyech gave Chelsea the lead midway through the first half of Wednesday’s game when he converted Kai Havertz’s cross into the box.
Villarreal almost leveled the score when Alberto Moreno thundered a volley off the crossbar on the stroke of halftime, and Gerard Moreno then also hit the woodwork at the start of the second half after Mendy’s slipped clearance and finger-tip save.
However, Villarreal did get its equalizer when Gerard Moreno scored from Boulaye Dia’s flicked backheel in the Chelsea box.
When the game advanced to penalties, Havertz’s opening effort was saved by Sergio Asenjo to hand Villarreal the advantage.
Gerard Moreno and César Azpilicueta then both scored, before Mandi’s penalty was saved by Kepa.
The game was ultimately decided in the second round of sudden death, when Antonio Rüdiger scored with an unconventional straight run up and Albiol was denied.
The Super Cup is contested at the start of each season between the reigning Champions League and Europa League champions.
“We were very strong in the first 30, 35 minutes, but then we lost some easy balls after our goal,” said Tuchel. “Second half, we were too passive, too many ball losses, and they deservedly equalized.
“From then until the end, we were very strong again. We invested more until the 120th minute and we deserved to win.”
The main blemish on the night for Chelsea was a shoulder injury for Ziyech in the first half — something Tuchel later described as “serious.”
His side begins its Premier League season against Crystal Palace on Saturday, while Villarreal plays Granada in La Liga on Monday.