The electrochemical CO₂ reduction reaction (CO₂RR) offers a dual benefit: closing the carbon cycle, while simultaneously storing renewable energy in chemical bonds. Carbon-based catalytic materials, as exceptional electrocatalysts, exhibit excellent conductivity, robust stability, tunable surface functionality, and unique capability to construct metal–carbon synergistic interfaces. In CO₂RR, carbon-based catalytic materials stand out duple critical functions among series roles: (i) active site engineering governing intrinsic activity, and (ii) mass/charge transport dictating effective active sites utilization. Synergistic optimization of these elements constitutes the “catalytic activity-transport kinetics” binary model for performance enhancement. This review dissects active sites design via defect engineering, heteroatom doping, and metal-carbon composites, coupled with mass/charge transport engineering through electronic conductivity modulation, surface hydrophobicity control, and hierarchical porosity optimization. We further critically examined the challenges and opportunities in CO₂RR, with a focus on the integrated design bottlenecks constraining high-performance catalyst development. By integrating these dual engineering paradigms, structure–performance correlations were established to guide the rational design of carbon-based CO₂RR catalysts.

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 *CO2·− and improved the selectivity of *CO2·− 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.