CO2 electrochemical reduction reaction (CO2RR) to formate is a hopeful pathway for reducing CO2 and producing high‐value chemicals, which needs highly selective catalysts with ultra‐broad potential windows to meet the industrial demands. Herein, the nanorod‐like bimetallic In2O3/Bi2O3 catalysts were successfully synthesized by pyrolysis of bimetallic InBi‐MOF precursors. The abundant oxygen vacancies generated from the lattice mismatch of Bi2O3 and In2O3 reduced the activation energy of CO2 to and improved the selectivity of to formate simultaneously. Meanwhile, the carbon skeleton derived from the pyrolysis of organic framework of InBi‐MOF provided a conductive network to accelerate the electrons transmission. The catalyst exhibited an ultra‐broad applied potential window of 1200 mV (from −0.4 to −1.6 V vs RHE), relativistic high Faradaic efficiency of formate (99.92%) and satisfactory stability after 30 h. The in situ FT‐IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO2 molecules, and oxygen vacancy path is dominant pathway. This work provides a convenient method to construct high‐performance bimetallic catalysts for the industrial application of CO2RR.