"Carbon peaking and carbon neutrality" is a major strategic decision made by our country to coordinate domestic and international situations. It is a solemn commitment to address prominent resource and environmental constraints and to build a community of human destiny. Carbon capture and storage (CCS), as a traditional carbon dioxide (CO2) control method, has potential leakage risk and a huge economic burden. In recent years, carbon capture, utilization and storage (CCUS) has been regarded as an effective alternative and supplement to CCS because it can convert the captured CO2 into value-added products for resource utilization. The development of efficient CO2 utilization technologies is the key to CCUS. Enzyme-catalyzed technology, as a typical green biomanufacturing technology, has received extensive attention in the field of CO2 utilization. The coupled catalytic systems based on enzyme catalysis open a rich pathway network for the resourceful conversion of CO2 into high-value chemicals or fuels. In this review, the "Enzyme +X" coupled catalytic systems for CO2 conversion in recent years was summarized and highlighted, including "Enzyme + Enzyme" coupled catalytic system, "Enzyme + Chemo" coupled catalytic system, "Enzyme + Photo" coupled catalytic system and "Enzyme + Electro" coupled catalytic system. The structures of different coupled catalytic systems were analyzed, and their system characteristics and catalytic processes were clarified. On the basis of structural analysis, the key to system module design and performance enhancement was discussed. The advantages and disadvantages of the "Enzyme + X" coupled catalytic system in CO2 resource conversion were expounded, and suggestions for its future development were provided. In an "Enzyme + Enzyme" coupled catalytic system, the pathway designability of CO2 conversion to target products is enriched, which can ensure the final products with higher value through the cascade reactions, thus greatly improving the economic efficiency. In an "Enzyme + Chemo" coupled catalytic system, the chemical catalytic process is usually applied to pre-convert CO2, after which the enzyme catalytic process directly uses C1 compounds as the starting materials, showing unique advantages in catalyzing the conversion of CO2 into C2/C2+ and other multi-carbon compounds. In an "Enzyme + Photo" coupled catalytic system, light energy is utilized by semiconducting materials to trigger the catalytic regeneration of coenzyme, avoiding the consumption of exogenous reduction equivalents in coenzyme-dependent enzymatic catalytic reactions. In an "Enzyme + Electro" coupled catalytic system, the electron transfer between the electrode and the enzyme can be regulated by altering the external bias voltage, which is rather crucial for driving the enzymatic hydrogenation in a high efficiency manner. The "Enzyme +X" coupled catalytic system can compensate for the drawbacks of the sole or single enzyme catalytic system to convert CO2 into energy-carrying compounds, which shows unique advantages and broad application prospects. However, the coupling of different catalytic systems increases the complexity of the system and requires precise construction of the coupled system. Meanwhile, the enzyme as a typical protein molecule may also affect the application of the "Enzyme +X" coupled system in some extreme external conditions. Although CO2 capture and storage is still the major strategy to achieve the goal of "carbon peaking and carbon neutrality" in near future, CO2 utilization technologies, including "Enzyme +X" coupled catalytic CO2 conversion technology, will gradually become a trend, which is expected to truly achieve the carbon neutralization goal the future.