CO 2 electroreduction is a promising technique for the management of the global carbon balance by low-grade renewable electricity. However, the lack of highly efficient and selective catalysts has hampered the development of this area. Herein, we report a poly-phenylenediamine-derived atomically dispersed Ni catalyst as a highly efficient and selective electrocatalyst for the conversion of CO 2 to CO. The catalyst facilitates efficient production of CO with high faradaic efficiency (FE) (90%) and a large current density of 11.6 mA cm −2 at −0.8 V compared to a reversible hydrogen electrode (RHE). An excellent turnover frequency (TOF) of 3079 h −1 for the electroreduction of CO 2 was also achieved at −0.8 V vs. RHE. A highly efficient atomically dispersed Ni catalyst for CO 2 electroreduction was synthesized by a simple and low-cost method.