M-N-C catalysts have considerable potential in the fields of catalysis, such as highly polluting gaseous elemental mercury (Hg0) oxidation. However, the direct application of these kinds of catalysts for mercury removal is stymied by their low catalytic efficiency. Heteroatom-doping in M-N-C catalysts has been proposed as a powerful strategy to the promote catalytic of Hg0, but the origin of boosting catalytic activity is still elusive. Herein, it is disclosed that selenium doping induces an obvious electron-acceptor effect for accelerating the Hg0 catalytic oxidation. The model selenium-doped Cu-N-C catalyst with atomically dispersed active sites was verified by various characterization methods, such as SEM-EDS and scanning transmission electron microscopy. The optimal Cu-NC-Se with Cu/Se ratio of 1:1 exhibited the best Hg0 removal performance, over 8-fold enhancement in their Hg0 oxidation capacities than raw selenium-free Cu-NC. At the optimal reaction temperature of 90 °C, Cu-NC-Se achieved an average Hg0 removal rate of 92.44% within 60 min under single pure N2 atmosphere. As for the influence of flue gas components, the presence of O2 promoted the removal of mercury in Cu-NC-Se, whereas CO2, NO and SO2 served as slight inhibitors. Even after five cycles of the experiment, the average mercury oxidization efficiency was still remained at 88.5%, showing that Cu-NC-Se can be reused with good maintenance of the catalytic activity and atomic dispersion of Cu and Se in the structure. The unsaturated Cu sites connected with pyridinic N on the carbon matrix can serve preferential adsorption to Hg0 and doped selenium. Meanwhile, the selenium doping accelerated Hg0 adsorption and accept sufficient electrons for promoting Hg0 oxidation to forming stable HgSe, which is also corroborated by the theoretical analysis results based on density functional theory. This work not only provides an alternative facile synthetic strategy for developing heteroatom-doping atomically dispersed M-N-C catalysts, but also represents a significant advance for deepening the understanding of the Hg0 catalytic oxidation mechanism on M-N-C catalyst.