Remarkably, Cu3Al2OF10 is highly active for the 8-electron NO3R, attaining upwards of 57% Faradaic Efficiency (FE) and 1220 A.g -1 mass activity. As such, this is the first oxyfluoride material applied towards NO3R. A complementary set of electroanalytical and operando spectroscopic investigations were carried out to elucidate that the Cu sites are indeed the active sites for the reaction and that the rate limiting step is the hydrogenation of the NHx reaction intermediate. The techniques developed and insights gained through this work should hasten the growth of this emerging area and thus bring NO3R closer to economic viability.