Rationally design and synthesize electrode materials with hollow nano-sphere (HNS) structures for high-performance flexible asymmetric supercapacitors (FASCs) still remains challenging. Herein, we developed a facile strategy for the construction of MnCo2O4 HNS. The unique hollow structure provided abundant open channels and redox active sites, shortening the ion diffusion path and facilitating the fast electrolyte transport. Moreover, due to the substantial multi-hierarchical pores in MnCo2O4 HNS, its specific surface area reached up to 110.15 m2 g−1. Subsequently, MnCo2O4 HNS as a battery-type material was grown on activated carbon cloth (ACC), and the resultant MnCo2O4 HNS/ACC electrode manifested high specific capacities. Furthermore, the MnCo2O4 HNS/ACC//ACC FASCs were fabricated, which exhibited remarkable electrochemical properties in terms of enhanced energy and power densities (0.78 mWh cm−3 at 9.78 mW cm−3) and superior mechanical flexibility. This work provides a new design of hollow nano-structures on carbon substrates, which can be a promising candidate for high-performance electrodes in FASCs.