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Ramos, 35, won four Champions League titles during a glittering 16-year spell at Real and has signed a two-year contract in Paris.
“This is a big change in my life, a new challenge and it’s a day I will never forget,” he said.
“Paris Saint-Germain is a club that has already proven itself at the highest level. I want to continue to grow and improve at Paris and help the team to win as many trophies as possible.”
A first Champions League win for PSG will be top of Ramos’ aims in Paris, where he joins former Liverpool midfielder Georginio Wijnaldum and ex-Inter right-back Achraf Hakimi as new signings.
Ramos scored more than 100 goals from centre-back for Real and has won a record 180 caps for Spain - though he was left out of his nation’s squad for Euro 2020.