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[References: 51 tit.]

Developing cost-effective carbon based electrocatalysts with high activity and selectivity for CO2 reduction reaction (CO2RR) at industrial current density still remains challenges. Herein, we present a metal-free 3D cross-linked carbon aerogel catalyst containing homogeneously dispersed N and P sites (P@NCA) synthesized via freeze drying and subsequent carbonization. Benefit from the synergistic effect of N and P atoms, P@NCA aerogel delivers an excellent CO2RR activity featured by a wide potential window from ? 0.3 V to ? 0.9 V with CO Faradaic efficiency (FE) of above 90 %. Importantly, a high CO FE of 85 % at an industrial current density of 100 mA cm?2 is realized. Experimental explorations and in-situ spectroelectrochemistry analyses reveal that pyrrolic-N species acts as the real active site to execute CO2RR, while the P species facilitates the protonation process of *CO2 to *COOH intermediate by accelerating the proton feeding from water dissociation. Theoretical calculations demonstrate a suppressed *H adsorption and a facilitated *CO desorption step on pyrrolic-N site with P doping, boosting the whole CO2RR process. Further, a rechargeable Zn-CO2 battery constructed with P@NCA aerogel as cathode delivers a maximal power density of 0.8 mW cm?2 and a superior stability.