The ever-increasing concentration of carbon dioxide (CO) in atmosphere has been resulting in disastrous effect on the nature and environment. Among the various methods for the CO reduction, the electrochemical reduction of CO (e-CORR) into fuels is considered to be much more effective. In this work, we find that the single atom catalysts (SACs) (SACs = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) can be firmly anchored on the N-terminated TiN(1 1 1) surface because of high binding energies on the basis of density-functional theory calculations. We show that the SACs on the N-terminate of TiN(1 1 1) can greatly reduce the energy barrier for e-CORR and improve the selectivity of products. SACs, including Sc, Ti, and V, show a high catalytic performance to produce CH with a low limiting potential of 0.68, 0.22, and 0.48 eV, respectively. Both CH and CHO can be obtained on SAC-Ni with the potential-determining step (PDS) of 0.77 eV. SAC-Cu can produce CH and CHOH. Our findings demonstrate that N-terminated surface is suitable for anchoring SACs and the catalytic performance for e-CORR, such as overpotential and selectivity, can be optimized by using different transition metals, which provides a great way for the convertion CO into fuels.