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Milan had lifted the Serie A title in 2004; Liverpool hadn't been domestic champions since 1990.
When veteran captain Paolo Maldini volleyed home the opener after a minute, and Hernan Crespo then scored a quick brace to put Milan 3-0 up before the break, it looked for all the world that the trophy would be heading to the San Siro.
The series of events that followed would defy all reason and logic, but somehow, it was Liverpool who ended the night as European champions, with captain Steven Gerrard hoisting the cup in front of more than 20,000 traveling fans.
Twenty years on, ESPN has spoken to Benitez, Liverpool winger Luis Garcia (now an ESPN pundit) and fans who made the 1,700-mile journey to Turkey to tell the story of the day, which will be forever known as "The Miracle of Istanbul."
Illustration by ESPNGetting to the game 'any way we could'
"We were the underdogs," said Garcia, who played the entire energy-sapping 120 minutes for Liverpool.
[Liverpool] had some really good players, but a few that probably weren't of the normal quality, let's say, to be in a Champions League final.
"Just to get to the final felt like an incredible achievement for this team, and we were determined to enjoy it."
One fan who was determined to soak up every moment of Liverpool's European odyssey was Kevin Walsh, who had to take three separate flights and two coach journeys to make it to Istanbul.
Roads were gridlocked, but Kevin Walsh made sure there was an atmosphere by lighting a flare out of their car. ESPN
"When we actually got to the final, it was a case of getting there in any way we could," he told ESPN.
"And at that stage, European Cup finals were things that my dad had told me about from the 1970s and 1980s, and I didn't think I was ever going to get to one if I'm being totally honest.
"So, to be walking into the ground as a Liverpool fan with my best mates, knowing that we were going to watch Liverpool potentially win the European Cup was an unbelievable experience."
Kevin Walsh with the Liverpool flags inside the ground. ESPNFirst-half horror
If Liverpool fans were on cloud nine before kickoff, it took only 50 seconds of match action for them to be brought firmly back down to earth, with Milan captain Maldini volleying in the opener from an Andrea Pirlo free kick.
2005 Champions League final teamsMilanLiverpoolDidaJ.
It wasn't a show of support, it was more of a show of defiance like: 'We're Liverpool Football Club and it's not gone our way today, but we're still Liverpool Football Club.'"
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How Liverpool fans' defiant 'You'll Never Walk Alone' powered 2005 comeback
Fans, pundits and players at the 2005 Champions League final remember what it was like to hear Liverpool's defiant rendition of 'You'll Never Walk Alone' at halftime in Istanbul.
Whether the song was intended as a rallying cry or not, its impact was quickly felt by the players.
Garcia said: "We had to try to score that first goal to give us hope to get back into the game, but the most important thing when we arrived for the second half was hearing 'You'll Never Walk Alone' from the supporters.
And so, by the time we got to extra time I remember just thinking: 'I'm so tired.' It was almost surreal, and we were all trying to piece together what we'd just seen because I'd never really seen anything like it.
"You just hoped there was one more twist in the tale and they could get some energy from somewhere and go on to win it."
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How Derek Rae called the moment Liverpool won the 2005 Champions League
Derek Rae, ESPN's lead commentator for the 2005 Champions League final, remembers his call of Jerzy Dudek's match-winning penalty save.
Both teams had chances to snatch the victory, but it was Liverpool goalkeeper Dudek who delivered the defining moment of the additional 30 minutes with his inexplicable double save to deny Shevchenko from close range in the 117th minute.
"I've had the opportunity to talk with Jerzy many times about that save, and I always ask him: 'How did you manage it?'" Garcia said.
I'm not one for saying our name is on the cup, but at that moment there was only one team that was going to win it."
'You couldn't write this story'
Having already made himself the standout, Dudek further enhanced his legendary status at Anfield with a memorable performance in the penalty shootout, deploying a host of distraction tactics, including mimicking Bruce Grobbelaar's "spaghetti legs" from the 1984 European Cup final against AS Roma in Rome.
Penalty shootoutMILANLIVERPOOLSerginho MISS (0-0)Hamann GOAL (0-1)Pirlo MISS (0-1)Cisse GOAL (0-2)Tomasson GOAL (1-2)Riise MISS (1-2)Kaka GOAL (2-2)Smicer GOAL (2-3)Shevchenko MISS (2-3)-
Dudek's antics had the desired effect, with Brazil international Serginho ballooning his effort over the bar, before saves from Pirlo and Shevchenko ensured the European Cup would be returning to Liverpool, the shootout score ending 3-2 to the Premier League team.
"The Milan players looked like they were walking to the guillotine because they had everything to lose," Gibbons said.