MnOx-CeO2 catalysts have shown great potential as selective catalytic reduction of NOx by NH3 (NH3-SCR) at temperature below 300 °C. While the improved catalytic activity due to the synergy between MnOx and CeO2 in MnOx-CeO2 catalysts is widely acknowledged, the synergistic mechanism in NH3-SCR reaction remains elusive due to the lack of direct evidences. In this study, we report a comprehensive study of how MnOx and CeO2 interacted during NH3-SCR in two designed MnOx-CeO2 catalysts with different Ce4+ concentration through both experimental and theoretical approaches. Our results reveal that electron transfer from Mn2+ to Ce4+ induced the formation of surface oxygen vacancy on the CeO2, leading to the synergistic promotion of low-temperature catalytic performance by establishing Mn-redox and Ce-redox cycles to activate NH3 and O2, respectively. This work provides a distinct mechanism diagram of the synergy between MnOx and CeO2, which sheds light on the rational design of low-temperature NH3-SCR catalysts.