But standing in their way are newly crowned English champions Arsenal.
Serial-winning mentor Enrique and his team, who also won the French league title, can stake the claim of being considered the greatest team of this era.
"I arrived at the club thinking, 'my objective is to make history,' and we have indeed made history," Enrique said. "We want to keep writing the story because we believe there's still more there for us to achieve."
PSG are already in the conversation when it comes to judging the finest teams to have won the title during the Champions League era. But sometimes cold, hard facts are required to drive the point home.
Victory at Puskas Arena would see PSG become only the second team to retain the trophy since the old European Cup was rebranded the Champions League in 1992.
For many years it didn't happen even for teams regarded as generationally great.
Pep Guardiola's Barcelona won two in three years. AC Milan and Juventus each reached three consecutive finals in the '90s but only won one apiece. Ajax and Manchester United took title defences all the way to the final only to fall at the last hurdle.
Real Madrid - winners of more European titles than any other club - finally bucked that trend, winning three in a row from 2016-18. What seemed unthinkable before and since would suddenly seem a very real target for PSG if they prevail.
Luis Enrique will join Guardiola and Zinedine Zidane as a three-time Champions League winner. Not that his motivation is based on personal accolades.
Having won the Champions League with Barcelona, Enrique has produced a PSG team that has set the benchmark in Europe over the past two seasons.
It combines attacking flair with an energy and tenacity that is moving the sport in a new direction. A team that plays with a high risk of being exposed defensively for the ultimate reward.
At their best, PSG seem unstoppable, with last year's 5-0 rout of Inter Milan in the final the most dominant in the tournament's 70-year history.
And with a squad that has an average age of under 24, the potential is there for them to dominate for years to come.
It is plain to see in PSG's performances - such as the 5-4 win over Bayern Munich in the semifinals - this is a special team, but titles are needed to confirm their status among the greatest.
Statistically, none can match Zinedine Zidane's Madrid team of Cristiano Ronaldo, Karim Benzema, Luka Modric and Toni Kroos that won three consecutive titles. Over a five-year period Madrid were European champions four times.
Overall, PSG has a long way to go to come close to Madrid's 15 titles, having won the Champions League for the first time last year. But they can stake their claim to be considered the best of their era.
A semi-final in Luis Enrique's first campaign was followed by last year's triumph and the chance to go back-to-back this season.
Arsenal, meanwhile, are aiming to pull off an upset and win their first Champions League title.
The Gunners advanced to the final after topping the league phase with a perfect winning record.
Mikel Arteta's team lost to PSG in last year's semifinals.
"It's two teams that are exceptional in the way they function, (how) they adapt and the intensity they play with," Arteta said. "We're going to have to be our best version to win it."
10°C