Touré, 43, took charge of the Slovak champions in July after leaving his role as an assistant with the Saudi Arabia national team, guiding Slovan through three qualifying rounds to reach the Champions League league phase for the first time in two years.
Wednesday's trip to face the reigning European champions marks the moment he becomes the first African-born coach to take charge of a team in the competition's history.
"It stirs up a slightly strange feeling, but at the same time it's also really nice on a personal level," Touré said at his pre-match press conference, according to AFP. He framed the achievement as part of a broader shift for coaches from the continent rather than simply a personal milestone.
"It's the start of a new, important era. We can finally say that a change is happening, and that we're looking ahead," he said.
The former Barcelona and Manchester City midfielder, who won the Champions League as a player with Barcelona in 2009, has followed a deliberately gradual path into coaching since retiring, working as an assistant at Ukrainian side Olimpik Donetsk, Russian club Akhmat Grozny, with Tottenham's youth setup and at Standard Liège before his most recent role with the Saudi national team.
He credited former Barcelona coach Frank Rijkaard, who gave him his breakthrough at the Camp Nou, as the biggest influence on his own coaching development, while also crediting Pep Guardiola for introducing him to the demands of positional play during his playing days.
Slovan, who have won the Slovak league for eight consecutive seasons under sporting director Robert Vittek, made a strong start to their domestic campaign this season, winning their first four league matches before back-to-back defeats ahead of the trip to Paris.
The club's only previous Champions League league-phase appearance ended in defeat in all eight matches, but Touré insisted there was no pressure on his side heading into a daunting assignment against a PSG team he described as being managed by "one of the best coaches around just now" in Luis Enrique.
Touré made 70 Champions League appearances during his playing career, making him the seventh-most capped African player in the competition's history.