Alves came to an agreement in principle with City and was poised to sign a two-year contract, only for the Ligue 1 club to offer improved terms.
The full-back underwent a medical in Paris on Tuesday and, prior to confirmation of the move, shared a telling post to his Instagram account.
“Humans are challenged,” the caption read. “Prepare to face without fear the consequences of your decisions, they will come filled with difficulties, but your confidence and your daily hard work will support you.
Alves added: “I am prepared for life since I was a boy, in my heart I have love and passion, in my soul an insatiable thirst to be a champion!”
The Brazil international is expected to be confirmed as a PSG player at a press conference on Wednesday afternoon.
Alves' U-turn will have come as a blow to Guardiola, who is attempting to revamp City's options at full-back this season having released Pablo Zabaleta, Gael Clichy and Bacary Sagna.
Kyle Walker, the Tottenham Hotspur right-back, remains a priority target, though the two clubs are still “sparring” over the fee.
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