The　development　of　new　synthetic　methods　for　methanol-tolerant　catalysts　with　improved　performance　is　of　fundamental　importance　for　the　commercialization　of　fuel　cells.　Herein,　we　reported　a　facile　displacement　reaction-assisted　synthesis　of　graphene-supported　sub-nanometer　Pt/Bi　catalysts　(Pt/Bi/rGO).　Bismuth　(0)　nanoparticles　produced　by　NH3BH3　reduction　can　be　further　dissolved　into　the　ethylene　glycol,　implying　Bi(0)　has　a　strong　interaction　with　the　hydroxyl　group.　That　is　the　key　interaction　between　Bi(0)　and　the　functional　group　on　the　rGO　to　form　the　ultra-small　Bi/rGO　catalyst.　Furthermore,　Pt　clusters　are　obtained　by　the　displacement　between　Bi(0)　and　HPtCl4　and　are　directly　anchored　to　the　rGO　surface.　The　as-synthesized　Pt/Bi/rGO　catalyst　exhibits　high　oxygen　reduction　mass　activity　and　high　tolerance　to　methanol　poisoning.　In　the　presence　of　0.5　mol/L　CH3OH,　the　initial　potential　and　activity　of　ORR　were　almost　unchanged,　which　demonstrated　great　potential　in　the　application　of　direct　methanol　fuel　cells.