An intriguingly nanostructured composite comprising of MnO/MnS nanoparticles embedded in an N,S-codoped carbon frame (MnO/MnS(@C) is designed here and employed as a promising Li-ion storage electrode material to address the challenge of inferior conductivity and large volume change toward manganese chalcogenide-based anode. Combining with the merits of coherent MnO/MnS, elaborately hierarchical-porous architecture and N,S-codoped carbon frame, this composite exhibits high lithium-ion storage capacity (591 mAh g(-1) at 0.1 A g(-1)) and remarkable cyclic performance (628 mAh g(-1) at 1 A g(-1) over 330 cycles). It is revealed via quantitative analysis that capacitive effect is also responsible for Li+ storage except ordinary diffusion-controlled mechanism, which consists of faradaic surface pseudocapacitance rooting from further oxidation of Mn2+ and nonfaradaic interfacial double-layer capacitance stemming from the charge separation at the MnO/MnS phase boundary. As a dynamic equilibrium for diffusion-controlled lithium storage, such capacitive contribution leads to ever-increasing Li-ion storage. The delicate construction endows an improved ion/electron transport kinetics, increased electrode/electrolyte contact area and plentifully heterogeneous interface, accounting for the high capacity and long-cycle stability.