Following a technical glitch that rocked the first Champions League draw on Monday, the French giants were paired with the record 13-time European champions.
The tie will see Ramos face a swift reunion with his former employers, whom he left in the summer after a 16-year trophy-laden spell.
Ramos joined PSG on a free transfer, signing a two-year contract, after his contract in the Spanish capital expired.
The 35-year-old made 671 appearances for Real Madrid in his time at the club, winning five La Liga titles with Los Blancos, four UEFA Champions League trophies, four FIFA Club World Cups, two Copa del Reys among numerous other honours.
"Fate is very unpredictable. I'd have liked us to draw another team, but that's how it is," Ramos said.
"You know the affection and love I have for Real Madrid, that won't ever change. Now I have to face the present. I play for PSG.
"It's a mixture of feelings. I'd have liked not to have had this tie, but on the other hand coming home to the Bernabeu, I had the best years of my life here and not having had a goodbye because of COVID, it's gratifying.
"I'd have liked it to be another way but that's football. I have to defend my team. I'll go to the death with PSG."
Ramos has only made one appearance for PSG since joining because of fitness issues.
