Perovskite oxides are proven as a striking platform for developing high‐performance electrocatalysts. Nonetheless, a significant portion of them show CO2 electroreduction (CO2RR) inertness. Here a simple but effective strategy is reported to activate inert perovskite oxides (e.g., SrTiO3) for CO2RR through slight Cu2+ doping in B‐sites. For the proof‐of‐concept catalysts of SrTi1−xCuxO3 (x = 0.025, 0.05, and 0.1), Cu2+ doping (even in trace amount, e.g., x = 0.025) can not only create active, stable CuO6 octahedra, increase electrochemical active surface area, and accelerate charge transfer, but also significantly regulate the electronic structure (e.g., up‐shifted band center) to promote activation/adsorption of reaction intermediates. Benefiting from these merits, the stable SrTi1−xCuxO3 catalysts feature great improvements (at least an order of magnitude) in CO2RR activity and selectivity for high‐order products (i.e., CH4 and C2+), compared to the SrTiO3 parent. This work provides a new avenue for the conversion of inert perovskite oxides into high‐performance electrocatalysts toward CO2RR.