CO2 reduction and resource utilization is an important means to alleviate Greenhouse Effect. Biocatalysts have high selectivity for reactions and substrates, so they are used to build efficient CO2 reduction systems. Among them, formate dehydrogenase (FDH) especially certain NAD⁺ -dependent/metal-containing (W- or Mo-) FDH are able to reversibly reduce CO2 to formate. This review summarizes the recent advances in reductive activity and catalytic mechanism of FDH for CO2 reduction, enzyme engineering, whole-cell biocatalysis and the application progress based on CO2 reductase. The innovative results summarized in this paper provide a great enlightenment and guidance for the future research of FDH for CO2 reduction, and provide a theoretical basis for the construction of feasible CO2 refining systems with abundant, cheap and sustainable CO2 as raw materials to produce value-added fuels and chemicals.