A facile soft templating strategy has been developed for synthesizing hollow spheres of nanocarbon by hydrothermal process. In this soft templating strategy, poly (ethylene oxide)–poly (propylene oxide)–poly (ethylene oxide) block co-polymers are used as the template while α-cyclodextrin are employed as the carbon precursor. After hydrothermal treatment, the soft templates can be easily removed by pyrolysis of the as-prepared hollow spheres in argon. The resultant hollow spheres of nanocarbon exhibit both micro- and meso-pores in carbon wall with a specific surface area of ∼380 m2 g−1. Upon incorporation of permanganate (MnO4 −) into the hollow carbon spheres, nanocrystalline manganese dioxide (MnO2) is grown on the carbon surface, where the redox reaction between carbon and MnO4 − takes place, giving rise to the formation of hollow carbon–MnO2 hybrid particles. An appropriate control in the diffusion of MnO4 − into the core of hollow carbon spheres, nanocrystalline MnO2 can be successfully grown on both the external and internal surfaces of the hollow carbon structure. The carbon–MnO2 hybrid spheres are demonstrated as a promising candidate material for supercapacitor application.