Electrocatalysis of CO2 toward multicarbon (C2+) products have multifaceted applications in the energy and chemical industries, offers an attractive route to mitigate carbon emissions and abate the depletion of fossil fuels. However, the productivity of CO2-to-C2+ products suffers from a low selectivity and reaction rate owing to the difficulty in C-C coupling and the multiple electron-proton transfer steps. Recently, numerous tandem catalysts have been developed to improve the selectivity and formation rate of CO2-to-C2+ products via coupled multiple reaction steps, exhibiting high industrial practicability. This review summarized recent progresses in the formation of C2+ products from CO2 electrolysis on tandem catalysts. In this review, we highlight the cooperative regulation strategy of tandem catalysts formed by introducing different types of new components and reveal the relationships between *CO intermediate mass transport and the selectivity of C2+ products. Moreover, theoretical insight into the tandem catalytic mechanisms underlying the enhanced C2+ selectivity is also provided. Finally, the remaining challenges and opportunities for the electrocatalytic CO2 toward C2+ products are discussed.