Urea is a valuable chemical feed stock that is commonly used in fertilizers and other industrial applications, including for the production of plastics and resins. Conventionally, industrial urea is produced through the reaction of ammonia and carbon dioxide under high pressure and temperature, resulting in intensive energy inputs and inefficiencies. In contrast, electrochemical synthesis of urea under mild conditions has been shown to be possible by coupled electrochemical reduction of CO₂ (CO2RR) and N₂ (NRR)¹. While finding active and efficient catalysts remains a major challenge, rational design can be advanced by identification of the favourable atomic arrangements that facilitate C-N bond formation. For this purpose, carbon-supported and nitrogen-coordinated metal single atom catalysts (SACs) are a promising class of electrocatalysts². Given their well-defined atomic structure, these material systems are valuable model systems for identifying active sites for specific reactions. Cu and Ni are well-known as efficient CO2RR catalysts^3,4, whereas Fe-based catalysts are traditionally used for N₂ fixation to produce NH₃ via the thermochemical Haber-Bosch method⁵. This background knowledge served as motivation for fabrication of two types of di-atomic catalysts (DACs), containing Cu-Fe and Ni-Fe components anchored in an electrochemically inert carbon framework. A wet-chemical method was used for synthesizing these materials. While no crystalline metallic reflections were observed in X-ray diffraction patterns, X-ray photoelectron spectroscopy confirmed the presence of constituent metals along with lattice N, O, and C. The X-ray absorption near edge structure (XANES) measurements of Fe, Ni and Cu edges show significantly different spectra when compared to corresponding metal foils and oxides. Importantly, a nitrogen-coordinated ‘single atom’ morphology with inter-metal interactions is confirmed by extended X-ray absorption fine structure (EXAFS). Electrochemical reduction reactions in the presence of CO₂ and N₂ showed formation of 2e^- CO2RR products, with CO dominant for the case of Ni-Fe DACs. In contrast, for the case of Cu-Fe DACs, formic acid generation was significantly more pronounced than CO. For the case of isolated NRR, NH₃ was observed for both DACs. The production of urea, however, was only observed for Cu-Fe DACs. While mechanistic investigations are underway, the primary difference in these activities is hypothesized to be due to formation of different intermediates and reaction paths followed during CO2RR. Previous studies⁶ have suggested that the choice of reaction path, CO₂→*OCHO→formic acid or CO₂→*COOH→CO, could be dependent on oxophilicity of the reaction site. Our observations indicate that C-N coupling is promoted by oxophilic CO2RR catalysts. Since the direct identification of active sites for coupled CO2RR and NRR has rarely been reported using simple ‘single atom’ based catalyst systems, our work opens up a new direction for designing catalysts capable of C-N coupling for the efficient generation of the valuable chemical, urea, under ambient conditions. References Chen, C., Zhu, X., Wen, X., Zhou, Y., Zhou, L., Li, H., Tao, L., Li, Q., Du, S., Liu, T. and Yan, D., Nat. Chem. 12, 717–724 (2020). Chen, Y., Ji, S., Chen, C., Peng, Q., Wang, D. and Li, Y., Joule 2, 1242–1264, (2018). Ferri, M., Delafontaine, L., Guo, S., Asset, T., Cristiani, P., Campisi, S., Gervasini, A. and Atanassov, P., ACS Energy Lett. 7, 2304–2310, (2022). Leverett, J., Yuwono, J.A., Kumar, P., Tran-Phu, T., Qu, J., Cairney, J., Wang, X., Simonov, A.N., Hocking, R.K., Johannessen, B. and Dai, L., ACS Energy Lett. 7, 920–928 (2022). Fuller, J., An, Q., Fortunelli, A. and Goddard III, W.A., Acc. Chem. Res. 55, 1124–1134 (2022). Feaster, J.T., Shi, C., Cave, E.R., Hatsukade, T., Abram, D.N., Kuhl, K.P., Hahn, C., Nørskov, J.K. and Jaramillo, T.F., ACS Catal. 7, 4822–4827 (2017).