AUltrafineamorphousNiBalloywaspreparedviachemicalreductionmethod;ItsstructuresduringthecrystallizatioinprecesswascharacterizedbysuchtechniquesasDifferentialthermalanalysis(DTA),X-rayabsorptionfinestructure(XAFS)andX-raydiffraction(XRD),andcorrelatedtothecatalyticpropertiesforbenzenehydrogenation.ItwasfoundthatthecrystallizationofamorphousNiBalloywascarriedoutintwosteps,asindicatedbytwoexothermicpeakscenteredat598and652Krespectively.Duringthefirststep.twometastablecrystallinephases,i.e.,Ni3BandanoaocrstallineNiphase(Ni-richNiBalloy),wereformed.Furtherannealingathighertemperatureof652KmayresultinthedecompositionofcrystallineNi3BandaggregationofnanocrystallineNi,thebenzenehydrogenationisoptimizedaroundtheannealingtemperatureof623K.ItmostprobablyresultsfromthemaximumamountofactivesiteonnanocrystallineNiformedbythermaltreatmentatappropriateannealingtemperature.