N,N-Dimethylformamide (DMF) is a widely used solvent, and its green and low-carbon synthesis methods are in high demand. Herein, we report a new approach for DMF synthesis using a continuous flow reaction system with a fixed-bed reactor and a ZnO-TiO2 solid solution catalyst. This catalyst effectively utilizes CO2, H2, and dimethylamine (DMA) as feedstocks, demonstrating performance with 99% DMF selectivity and single-pass DMA conversion approaching thermodynamic equilibrium. Moreover, the catalyst demonstrates good stability, with no signs of deactivation over 1000 h of continuous operation. The key to superior activity lies in the synergetic effect of the Zn and Ti sites, which facilitates the formation of active formate species. These species act as crucial intermediates, reacting with DMA to produce DMF. Importantly, the slow hydrogenation kinetics of the formate species prevent the formation of CH2O* species, thereby suppressing the formation of the undesired byproduct, trimethylamine. This work underscores the potential of kinetically controlling active intermediates in CO2 hydrogenation to prepare high-value-added chemicals by coupling them to platform molecules. It presents a promising strategy for the efficient utilization of CO2 resources and offers a valuable solution for large-scale DMF synthesis.