In this paper, effect of heat treatment on the microstructures and wear properties of laser alloying (LA) composites is investigated. LA of the T - Co 50/ FeSi / TiC / TiN / CeO 2 mixed powders on substrate of 45 steel can form the hard composites, which increased the wear resistance of substrate greatly. Such LA composites were investigated by means of a scanning electron microscope (SEM) and a transmission electron microscope (TEM). The tempering promoted the growth of the block-shape hard phases, favoring an enhancement of the integrity of block-shape hard phases; and tempering also improved greatly the formation mechanism, guarantying the composites to have enough ability of intensity transfer. This research provided essential experiment and theoretical basis to promote the application of the laser and heat treatment technologies in the field of surface modification.