The variations of microhardness with the composition, heat treatment and structure have been studied by measuring microhardness and analyzing X-ray diffraction spectrum for electroless plating Fe-W-B crystallization and Fe-Mo-B amorphous alloys The results show that the microhardness of two alloy systems increases with increasing metalloid B contents, which is opposite to the electronic concentration The microhardness of Fe-W-B deposit has the peak value with increasing annealing temperature,which concerns with the phase type and number of crystallizable separation out