Amorphization induced by sliding wear and consequent wear resistance have been investigated in relation with the microstructure of Fe-Cr-B alloy spray coatings. The Fe-Cr-B spray coated layer exhibited much higher wear resistance and significantly lower friction coefficient in comparison with that of low carbon steel substrate thanks to the amorphous surface film formed during the dry sliding wear. Electron microscopy on the cross-section of the coated layer exhibited intra-particle segregation associated with rod-shape Cr rich (Cr,Fe)xB particles in the matrix of Fe-Cr solid solution phase. From the observations using TEM and EDS, Fe-Cr solid solution phase with super-saturated Band Si content was confirmed to be the phase which mainly contribute to the crystalline-to-amorphous transition induced by sliding wear. The formation of oxide inclusions, seems to impede the crystalline-to- amorphous transition by lowering the solute content in Fe-Cr solid solution phase.