The catalytic performances of different CuZnAl catalysts prepared using copper nitrate, copper acetate and copper citrate for CO hydrogenation to higher alcohols (C2+OH) were studied in a slurry bed reactor. Among these catalysts, the Cu-N catalyst prepared using copper nitrate showed a relatively higher C2+OH selectivity and no obvious deactivation occurred during the lifetime test for 120 h. The influence of copper precursors on the performance of the CuZnAl catalysts was investigated by XRD, 27Al-MAS-NMR, N2 adsorption-desorption, H2-TPR, NH3-TPD, FT-IR and XPS techniques. The results indicated that the size of Cu0 particles, textural properties, the chemical state of Cu species, the amount of surface acid and chemical composition varied, which led to diverse catalytic activities toward C2+OH synthesis. It was concluded that Cu0, Cu+ and AlOOH were all necessary in ethanol and C2+OH synthesis when using the CuZnAl catalysts without promoters and the synergism of these species was beneficial to the formation of C2+OH. This work further demonstrated that alkalis and Fischer-Tropsch elements were not indispensable for C2+OH synthesis from syngas.