The Canadian is through to the second round after a tricky three set win in his opening match.
Felix Auger-Aliassime will meet Alexander Zverev in the Madrid quarter-finals.
After losing to his Canadian rival last week, Rublev has turn the tables to win his first Tour title in almost a year.
Felix Auger-Aliassime was the main focus in the latest rankings that were released on Monday after winning Rotterdam.
The Canadian controlled the game from start to finish en route to winning the trophy.
Sunday's final will see Auger-Aliassime bid to win his maiden Tour title. Meanwhile, Tsitsipas will be seeking to claim his first at a ATP 500 event.
Auger-Aliassime is among four seeded players to reach the last eight in Rotterdam.
The Canadian managed to pull off an impressive comeback against his Belorussian opponent to reach the next round.
Daniil Medvedev saved match point and came from two sets to love down to defeat Felix Auger-Aliassime and reach the Australian Open semi-finals.
The Montreal native became the second Canadian to reach the quarterfinals at the Australian Open after winning in four sets.
Felix Auger-Aliassime is into the last 16 of the Australian Open after a dominant performance against Dan Evans.
For a second time this week the Canadian was pushed but managed to win a tough four-set match against his Spanish opponent.
Felix Auger-Aliassime inspired Canada to victory against Great Britain at the ATP Cup.
The two tennis stars cited fatigue and injury as the reason why they have chosen not to play in the team event.
The Canadian was pushed to the limits by his Italian counterpart but managed to pull through.
Matteo Berrettini contributed to a 3-1 overall scoreline for Team Europe over Team World after day one of the Laver Cup.
