www.afm-journal.de© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim1904206 (1 of 7)Li–CO2 batteries are an attractive technology for converting CO2 into energy. However, the decomposition of insulating Li2CO3 on the cathode during discharge is a barrier to practical application. Here, it is demonstrated that a high loading of single Co atoms (≈5.3%) anchored on graphene oxide (adjacent Co/GO) acts as an efficient and durable electrocatalyst for Li–CO2batteries. This targeted dispersion of atomic Co provides catalytically adjacent active sites to decompose Li2CO3. The adjacent Co/GO exhibits a highly significant sustained discharge capacity of 17 358 mA h g−1 at 100 mA g−1 for >100 cycles. Density functional theory simulations confirm that the adjacent Co electrocatalyst possesses the best performance toward the decomposition of Li2CO3 and maintains metallic-like nature after the adsorption of Li2CO3.