Poly(N-vinyl-2-pyrrolidone)　(PVP)-protected　Au/Ni　bimetallic　nanoparticles　(BNPs)　were　prepared　using　a　chemical　reduction　method.　The　obtained　BNPs　were　characterized　by　Ultraviolet-visible　spectrophotometry　(UV-Vis)　and　transmission　electron　microscopy　(TEM).　The　effects　of　metal　compositions　on　the　hydrolysis　reaction　of　the　alkaline　NaBH4　solution　were　studied.　The　results　indicate　that　the　prepared　Au/Ni　BNPs　have　an　average　size　of　2.9　similar　to　4.2　nm.　The　activities　of　BNPs　are　much　higher　than　that　of　Au　and　Ni　monometallic　nanoparticles　(MNPs).　Among　all　the　MNPs　and　BNPs,　Au/Ni　BNPs　with　atomic　ratio　of　50/50　display　the　highest　catalytic　activity,　showing　a　high　hydrogen　release　rate　of　550　mol-H-2.h(-1).mol-M-1　at　30　degrees　C.　The　catalytic　activity　of　the　Au/Ni　BNPs　higher　than　that　of　corresponding　MNPs　can　be　ascribed　to　electronic　charge　transfer　effects.　X-ray　photoelectron　spectroscopy　(XPS)　and　density　functional　theory　(DFT)　show　that　Au　atoms　are　indeed　negatively　charged,　while　the　Ni　atoms　have　positive　charges　due　to　the　electron　donation　from　the　Ni　atoms　to　Au　atoms.　The　positively　charged　Ni　atoms　and　negatively　charged　Au　atoms　act　as　catalytic　active　sites　for　the　hydrolysis　reaction　of　the　alkaline　NaBH4　solution.　Au50Ni50　BNPs　display　a　low　apparent　activation　energy　of　61.9　kJ/mol.