Trimetallic Co-Ni-Cu catalyst from perovskite precursor was prepared by co-precipitation method and then examined for its ability to form higher alcohols from syngas. A superior C2+ OH yield of 142.1 mg.g(cat.)(-1).h(-1) was achieved at 315 degrees C, H-2/CO = 2, P = 3.0 MPa and GHSV of 10,995 mg.g(cat.)(-1).h(-1), which was almost two times higher than that obtained with monometallic Co and bimetallic Co-Ni perovskite catalysts. The addition of Cu alters the electronic interactions with the Co and Ni species, thereby promoting the reduction of perovskite catalysts and forming Co-Ni-Cu alloy after reduction. It was found that the substitution of Cu facilitated the formation of Co2C species during the reaction. Both Co-Ni-Cu alloy and Co2C species were observed in the spent catalyst, suggesting that the formation of Co-Ni-Cu alloy and Co-Co2C interface play key roles in the improvement of higher alcohol formation.