The tungsten carbide catalysts supported on carbon nanotubes were prepared by the temperature-programmed reduction, and there were used as catalysts for the hydrogenation of cellulose. The optimum synthesis and reactive conditions were investigated. The results show that the WC loading was 40%, the catalyst calcination temperature was 773K, the reduction temperature was 1073K. The conversion rate of cellulose could reach 84.5%, and the yield of sorbitol was 45.9%. The WC/CNTs catalysts show high catalytic activities and higher selectivity towards sorbitol in crystal cellulose hydrogenation.