The chloroplatinic acid, nickel chloride and cobalt nitrate, as raw materials, are used to synthesize PtCoNi alloy nanoparticles with well dispersion loaded on xc-72 carbon black by spray drying method combined with calcination reduction. The influence of the surface of the carbon black on the formation and dispersion alloy nanoparticles was studied, and the effects of PtCoNi with the same atomic ratio and PtCoNi with different atomic ratio on methanol catalytic oxidation activity and CO poisoning resistance and durability were investigated in detail. The results showed that PtCoNi catalyst loaded on surface modified carbon black is alloy nanoparticles, and the nanoparticles are dispersed evenly on the surface of carbon black with particle size distribution of 1-4nm and average particle size of 2.3nm. Compared with commercial Pt/C catalysts, PtCoNi/C with the same atomic ratio has higher catalytic methanol oxidation activity, durability and CO poisoning resistance. The order of activity of PtCoNi catalysts with different atomic ratio in catalytic methanol oxidation reaction is :PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C, and the sequence of CO poisoning resistance is PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C.