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Solid oxide carbon dioxide electrolysers are expected to play a key role in carbon-neutral energy landscape.However,the limited activity of traditional ceramic cathodes still restricts the electrochemical performance.Here we report the doping of Mn at the B site of SrFeO3-δ cathode to improve CO2 electrolysis.The oxygen vacancy concentration is increased by ～30％ with Mn doping while the surface oxygen exchange coefficients are enhanced by ～10 times.The chemisorption of CO2 indicates the presence of chemical intermediate state between CO2 molecule and carbonate ion on the oxygen-deficient cathode surface which therefore leads to the desorption temperature of～800 ℃.The Mn-doped SrFeO3-δ enhances CO2 electrolysis with no performance degradation being observed even after high-temperature operation of 100 hours.