Display omitted •Cu/CeO2 catalysts were prepared using different impregnation orders for Cu and Ce.•Cu–Ce/CeO2 (prepared by co-impregnation) exhibited the highest catalytic activity.•Cu dispersion and Cu particle size are important factors in reaction < 280 °C.•Oxygen vacancy concentration and active Cu species are important factors > 360 °C. To investigate the effect of Cu/CeO2 catalysts preparation methods for low temperature water−gas shift reaction, Cu/CeO2 catalysts were prepared with various impregnation sequences and applied to the water−gas shift reaction at a high gas hourly space velocity of 36,080 mL/g·h. The catalyst preparation method affected both the Cu−Ce synergistic effect and the physico−chemical properties of the Ce promoted Cu/CeO2 catalysts, such as specific surface area, Cu particle size, Cu dispersion, amount of active Cu species and oxygen vacancy concentration. Among the prepared catalysts, Cu–Ce/CeO2 showed the highest CO conversion because of the high contents of active Cu species and high concentration of oxygen vacancies.