Poly(N-vinyl-2-pyrrolidone)(PVP)-protected　Au/Ni　bimetallic　nanoparticles　(BNPs)　were　prepared　in　one-vessel　via　chemical　reduction　of　the　corresponding　ions　with　dropwise　addition　of　NaBH4,　and　their　catalytic　activity　in　the　hydrogen　generation　from　hydrolysis　of　a　basic　NaBH4　solution　was　examined.　The　structure,　particle　size,　and　chemical　composition　of　the　resultant　BNPs　were　characterized　by　Ultraviolet　visible　spectrophotometry　(UV-Vis),　X-ray　photoelectron　spectroscopy　(XPS),　Transmission　electron　microscopy　(TEM)　and　High-resolution　transmission　electron　microscopy　(HR-TEM).　The　effects　of　processing　parameters　such　as　metal　composition,　metal　ion　concentration,　and　mole　ratio　of　PVP　to　metal　ion　on　the　hydrolysis　of　a　basic　NaBH4　solution　were　studied　in　detail.　The　results　indicated　that　as-prepared　Au/Ni　BNPs　showed　a　higher　catalytic　activity　than　corresponding　monometallic　NPs　(MNPs)　in　the　hydrogen　generation　from　the　hydrolysis　reaction　of　a　basic　NaBH4　solution.　Among　all　the　MNPs　and　BNPs,　Au/Ni　BNPs　with　the　atomic　ratio　of　50/50　exhibited　the　highest　catalytic　activity,　showing　a　hydrogen　generation　rate　as　high　as　2597　mL-H-2　min(-1)　g-catalyst(-1)　at　30　degrees　C,　which　can　be　ascribed　to　the　presence　of　negatively　charged　Au　atoms　and　positively　charged　Ni　atoms.　Based　on　the　kinetic　study　of　the　hydrogen　generation　from　the　hydrolysis　reaction　of　a　basic　NaBH4　solution　over　the　PVP-protected　Au/Ni　BNPs,　the　corresponding　apparent　activation　energy　was　determined　as　30.3　kJ/mol　for　the　BNPs　with　the　atomic　ratio　of　50/50.　Copyright　(C)　2013,　Hydrogen　Energy　Publications,　LLC.　Published　by　Elsevier　Ltd.　All　rights　reserved.