Conversion of methane to ethylene with high yield remains a fundamental challenge due to the low ethylene selectivity, severe carbon deposition and instability of catalysts. Here we demonstrate a conceptually different process of in situ electrochemical oxidation of methane to ethylene in a solid oxide electrolyzer under ambient pressure at 850 °C. The porous electrode scaffold with an in situ-grown metal/oxide interface enhances coking resistance and catalyst stability at high temperatures. The highest C2 product selectivity of 81.2% together with the highest C2 product concentration of 16.7% in output gas (12.1% ethylene and 4.6% ethane) is achieved while the methane conversion reaches as high as 41% in the initial pass. This strategy provides an optimal performance with no obvious degradation being observed after 100 h of high temperature operation and 10 redox cycles, suggesting a reliable electrochemical process for conversion of methane into valuable chemicals.

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