A series of CuxCoy catalysts were successfully synthesized by deposition-precipitation with urea method and their catalytic performance was investigated for methanol decomposition to hydrogen. These as-prepared samples were characterized by ICP-OES, XRD, SEM, BET, H-2-TPR and XPS. The characterization results indicate that the bimetallic catalysts exhibit better dispersion and reducibility as compared with the monometallic catalysts, and the strong interaction between copper and cobalt can promote the formation of Cu+. Among the fabricated materials, the Cu0.5Co0.5 presents the best catalytic activity and H-2 selectivity. Moreover, its catalytic performance is higher than the commercial catalyst at the same test conditions.Graphical AbstractThe catalytic performance of bimetallic CuxCoy catalytic is better than that of monometallic catalysts. Meanwhile, the optimized catalyst prepared exhibits excellent catalytic activity and selectivity compared with the commercial catalysts at the same reaction conditions, which is due to the coexist of Cu+ and Cu2+ after reduction. [GRAPHICS] .