© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Metal–CO2 batteries have attracted much attention owing to their high energy density and use of greenhouse CO2 waste as the energy source. However, the increasing cost of lithium and the low discharge potential of Na–CO2 batteries create obstacles for practical applications of Li/Na–CO2 batteries. Recently, earth-abundant potassium ions have attracted considerable interest as fast ionic charge carriers for electrochemical energy storage. Herein, we report the first K–CO2 battery with a carbon-based metal-free electrocatalyst. The battery shows a higher theoretical discharge potential (E⊖=2.48 V) than that of Na–CO2 batteries (E⊖=2.35 V) and can operate for more than 250 cycles (1500 h) with a cutoff capacity of 300 mA h g−1. Combined DFT calculations and experimental observations revealed a reaction mechanism involving the reversible formation and decomposition of P121/c1-type K2CO3 at the efficient carbon-based catalyst.