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A first-half goal from Brazilian international Igor Jesus proved the difference as Botafogo all but sealed a place in the knockout rounds in front of a 53,699 crowd at the Pasadena Rose Bowl.
French champions PSG are widely regarded as one of the favourites for FIFA's 32-team tournament after a dazzling season which culminated with a scintillating 5-0 demolition of Inter Milan in the Champions League final last month.
But their hopes of securing a victory which would have seen them become the first side to reach the last 16 were stymied by a resilient performance from their opponents from Rio de Janeiro.
"A lot of people wondered, but we showed how strong Botafogo are," goalscorer Jesus said after the win. "It was a difficult game, and we had to defend well, and we did our job and scored a goal.
