Abstract Developing effective catalysts based on earth abundant elements is critical for CO 2 electroreduction. However, simultaneously achieving a high Faradaic efficiency (FE) and high current density of CO ( j CO ) remains a challenge. Herein, we prepare a Mn single-atom catalyst (SAC) with a Mn-N 3 site embedded in graphitic carbon nitride. The prepared catalyst exhibits a 98.8% CO FE with a j CO of 14.0 mA cm −2 at a low overpotential of 0.44 V in aqueous electrolyte, outperforming all reported Mn SACs. Moreover, a higher j CO of 29.7 mA cm −2 is obtained in an ionic liquid electrolyte at 0.62 V overpotential. In situ X-ray absorption spectra and density functional theory calculations demonstrate that the remarkable performance of the catalyst is attributed to the Mn-N 3 site, which facilitates the formation of the key intermediate COOH * through a lowered free energy barrier.