The shale gas revolution bolsters ethane supply, thereby enhancing the economic viability of ethylene production from ethane. Presently, catalytic ethane dehydrogenation technology exhibits immense potential in the realm of ethylene production. This study achieves the electrochemical oxidative dehydrogenation conversion of ethane to ethylene via a solid oxide electrolysis cell (SOEC), effectively circumventing the issue of excessive oxidation during the ethane oxidative dehydrogenation process. An active electrode with an in situ grown metal-oxide interface significantly promotes the activation of the ethane C–H bond, leading to efficient ethylene production. Under the co-electrolysis mode of ethane with CO2, the Co@CeO2 electrode demonstrates exceptional performance, achieving an ethane conversion rate of 33.1% and an ethylene selectivity of 88.9% at an applied voltage of 1.0 V. Moreover, the metal-oxide interface constructed via an in situ exsolved method effectively prevents the agglomeration of nanoparticles at high temperatures, thus enhancing the catalyst's resistance to coking and stability. Notably, the electrode's performance does not exhibit significant degradation even after 100 h of electrochemical reaction.