Abstract Electrochemical features and the charge‐storage mechanism of monodispersed MnO nanoparticles anchored on graphite (MnO@Graphite) for Li‐ion batteries have been investigated at a low‐temperature of −25 °C. MnO@Graphite nanocomposite rendered a remarkable reversible capacity of 456 mA h g −1 after 320 cycles under a current density of 100 mA g −1 at such a low temperature. Remarkable reversible capacity could be ascribed to the integrated structure, emergence of in‐situ formed MnO 2 and hybrid pseudocapacitance. Hybrid pseudocapacitive contributions have appeared at low operational temperature, i. e., assembled heterogeneous intercalation pseudocapacitance at low potentials and surface‐controlled pseudocapacitance at high potentials. The results showed that the prepared MnO@Graphite nanocomposite is a promising candidate for Li‐ion batteries operated in harsh environment.