The introduction of oxophilic metals can enhance the selectivity of CO2 reduction reactions (CO2RR) by modulating the adsorption of oxygen-associated active substances on the catalyst surface. Alloying lanthanide atoms into metals has been shown to improve CH4 selectivity by breaking the linear relationship between the adsorption energies of CO* and HxCO*. In this work, a series of oxophilic transition metals (Fe, Mo, Co, Mn) are introduced to explore the influence on the CO2RR. DFT results demonstrate that the doping of oxophilic metals regulates the adsorption strength between the catalyst surface and intermediates, thereby affecting the CH4 and H3COH pathways. Notably, COOH* formation is enhanced on Ni surfaces, leading to increased H3COH production. Ni-Fe and Ni-Mo exhibit significant H3CO* and CO2* binding energies, which reduces the barrier for H3CO*. Meanwhile, the bond energy of M−O is higher than that of C-O in H3CO*, promoting the generation of CH4. The addition of Co and Mn makes the desorbed of HCOOH smaller than the hydrogenation energy barrier, which accelerates the synthesis of formic acid. This research provides a new pathway for the development of inexpensive and resource-rich catalysts.