Li-doped CuFeO2 thin films are fabricated by electrodeposition and their photoelectrocatalytic performance for CO2 reduction is examined. CuFeO2, LiFeO2, Cu2O and CuO are observed in Li-doped CuFeO2 thin films. At Li-doped CuFeO2 thin film photocathodes, CO2 can be reduced to methanol with high selectivity. At the overpotential of 110 mV, methanol concentration is up to 153.75 mu M and faradaic efficiency of methanol is as high as 96.7% in 1.5 h at the photocathode electrodeposited at -1.00 V. Since adsorbed CO has low mobility on LiFeO2 surface, CO coupling on the electrode surface is inhibited, thus no C2+ products are formed. (C) 2019 The Electrochemical Society.