Herein, we report a simple approach to synthesize CuFeO2/TNNTs photocathodes composed of high-temperature resistance n-type Nb-doped TiO2 nanotube arrays (TNNTs) and p-type CuFeO2 for CO2 reduction. TNNTs were prepared by anodic oxidation on TiNb alloy sheets and CuFeO2/TNNTs were then prepared by coating precursor liquid onto TNNTs followed by heat treatment in argon atmosphere. The microstructures of CuFeO2/TNNTs and TNNTs before and after heat treatment were investigated by SEM and TEM. The phase compositions of CuFeO2/TNNTs were studied by XRD and XPS, and the light absorption performance were tested by UV-vis diffuse reflectance spectrum. Results show that TNNTs exhibit a regular nanotube arrays structure and this structure is well remained after the calcination at 650 degrees C. In addition, TNNTs show similar semiconductor properties to n-type TiO2, which enables them to be integrated with p-type CuFeO2 to obtain composite photocathodes with a p-n junction. The synthesized CuFeO2/TNNTs photocathode is well crystallized because no other crystalline iron or copper compounds are included in the prepared photocathode. Furthermore, the photocathode shows high light absorption and fast carrier transport due to the appropriate band gap and p-n junction. As a result, high photoelectrocatalytic CO2 reduction performance with high selectivity to ethanol is obtained on this photocathode. (C) 2020 Elsevier Inc. All rights reserved.