Abstract 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·gcat.−1·h−1 was achieved at 315 °C, H2/CO = 2, P = 3.0 MPa and GHSV of 10,995 ml·gcat−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.