Heterostructures show excellent performance in energy and environment fields due to the unique interface structure and synergistic effect of multi-components. Here, we introduce a stepwise method to prepare multi-element Co3O4@C@MnO2 heterostructures on nickel foam as binder-free supercapacitor electrode material, where crystalline Co3O4 acts as intimal "core" and wrinkled ultrathin MnO2 nanosheets as the outer "shell". In three-electrode mode, Co3O4@C@MnO2 shows excellent electrochemical performance with a high cyclic specific capacitance of 1335.3 Fg(-1) at a current density of 20 A g(-1). Furthermore, the asymmetry supercapacitor device assembled with Co3O4@C@MnO2 heterostructures and active carbon exhibits high specific capacity (126.6Fg(-1) at a current density of 0.5Ag(-1)) and long life (about 61 Fg(-1) at a relatively high current of 20Ag(-1) after 40,000 cycles). Compared with Co3O4@MnO2 or C@MnO2, the improved performance of Co3O4@C@MnO2 heterostructures is proposed to be attributed to the synergistic effect in multi-components. Remarkably, the introduction of C between Co3O4 and MnO2 could promote the electron transfer, reduce the impedance and thus improve the electrochemical performance of the heterostructures. (C) 2018 Elsevier Ltd. All rights reserved.