jats:titleAbstract</jats:title>jats:pElectrochemical reduction of COjats:sub2</jats:sub> provides an opportunity to reach a carbon‐neutral energy recycling regime, in which COjats:sub2</jats:sub> emissions from fuel use are collected and converted back to fuels. The reduction of COjats:sub2</jats:sub> to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for COjats:sub2</jats:sub> conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for COjats:sub2</jats:sub> reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The COjats:sub2</jats:sub> reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–Njats:sub4</jats:sub>) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.</jats:p>