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Very recently, open-cage metallo-azafullerenes PbC100N4H4 and Pb2C100N4H4 containing one Pb–N4–C moiety have been synthesized via the electron beam. Herein, we utilized density functional theory calculations in combination with ab initio molecular dynamics (AIMD) simulations to study the geometric and electronic structures, bonding properties, thermodynamic stability, and catalytic performance of MC100N4H4 and M2C100N4H4 (M = Ge, Sn, Pb). Metal–nitrogen distances and metal–metal distances increase along with the metal radius while the metal atom is positively charged. Energy decomposition analysis revealed that the bonding interactions between M and the C100N4H4 fragment could be described as the donor–acceptor interaction between M(ns0(n−1)d10np4) and C100N4H4 fragment, in which the orbital interactions terms contribute more than the electrostatic interactions. AIMD simulations demonstrate that those metallo-azafullerenes exhibit thermodynamic stability at room temperature. These metallo-azafullerenes, which could serve as typical carbon-supported single-atom catalysts, possess enhanced catalytic performance toward the oxygen reduction reaction (ORR) compared to the planar catalysts, which is attributed to the curvature of metallo-azafullerenes. GeC100N4H4 and SnC100N4H4 exhibit high catalytic performance in the 4e-ORR pathway to H2O, whereas only PbC100N4H4 is suitable for the 2e-ORR reaction pathway because of the difficulty in obtaining electrons. All M2C100N4H4 favors the 4e-reaction pathway due to the presence of the axial metal atom. Our finding of open-cage metallo-azafullerenes as efficient single-atom catalysts holds profound implications for both fundamental research in catalysis and practical applications in fuel cells and other electrochemical devices. [ABSTRACT FROM AUTHOR]