Understanding the surface defect chemistry of oxides has proven to be highly important in electrochemical oxidation. V2O5 nanorods (NRs) were loaded onto porous Ti membranes, then treated with H2 to generate reduced defect-rich V2O5 NRs/Ti (r-V2O5 NRs/Ti) electrodes. These r-V2O5 NRs/Ti electrodes were used to construct an electrocatalytic membrane reactor (ECMR) for the electro-oxidation of cyclohexane (CHA) to cyclohexanone (K) and cyclohexanol (A). The electrocatalytic results showed that the r-V2O5 NRs/Ti membrane electrode exhibited superior catalytic performance compared with the original V2O5 NRs catalyst. 55.5% conversion and more than 99% selectivity were obtained at 30 degrees C and ambient pressure without any oxidant, which is superior to most catalysts reported in the literature. More importantly, density functional theory (DFT) calculations confirmed that the existence of oxygen vacancies on the r-V2O5 NRs/Ti electrode led to the lower band gap facilitated electron transition, resulting in enhanced conductivity and superior electrochemical activity. (C) 2020 Elsevier Inc. All rights reserved.