Ni-Mo promoted Cu/CeO2 catalyst was synthesized by co-precipitation method using 28%wt NH3·H2O as the precipitant. The catalysts were characterized by BET, XRD, TPR and XPS. The results showed that Ni and Mo could promote the reducibility of Cu, and the interaction between Ni and Mo may be needed for catalytic activity and higher alcohols synthesis. Therefore, CuNiMo/CeO2 catalyst showed a higher activity for higher alcohols synthesis than Cu/CeO2. In the meantime, the effect of pyrogallol used in preparing the CuNiMo/CeO2 catalyst was investigated. Pyrogallol had a significant influence on lowering the methanol selectivity and improving the C2+-OH selectivity. The methanol selectivity decreased from 52.99% to 44.81% and SC2+OH/SMeOH (MeOH denoted as methanol) ratio increased from 0.27 to 0.35. The XPS results gave evidence that pyrogallol can form complexes with Cu+ on the CeO2 support, which causes methanol decrease. In addition, pyrogallol could serve as a “temperature addictive agent” to save power.