The electrochemical reduction of carbon dioxide and nitrite ions into value-added chemicals represents one of the most promising approaches to relieve the greenhouse gases, while a critical challenge is to search for a highly effective catalyst with low energy input and high conversion selectivity. In this work, we demonstrated low-valence Cu doped, oxygen vacancy-rich anatase TiO2 (Cu-TiO2) nanotubes as a synergetic catalyst for electrochemical co-reduction of both CO2 and NO2-. The incorporation of Cu dopants in anatase TiO2 facilitated to form abundant oxygen vacancies and defect sites, which allowed for efficient nitrite adsorption and activation. The low-valence Cu dopants also served as effective catalytic centers to reduce CO2 into CO* adsorbate. The close proximity of CO* and NH2* intermediates was beneficial for the subsequent cooperative tandem reaction to form urea via the C-N coupling. This oxygen vacancy-rich Cu-TiO2 electrocatalyst enabled excellent urea production rate (20.8 mu mol.h(-1)) and corresponding Faradaic efficiency (43.1%) at a low overpotential of -0.4 V versus reversible hydrogen electrode, substantially superior than those of undoped TiO2, thus suggesting an exciting approach for cooperative CO2 and nitrogen fixation. (C) 2020 Elsevier Inc. All rights reserved.