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We have demonstrated a facile and controllable synthesis of N-doped carbon spheres by an amine-induced Stöber-silica/carbon assembly route. In this process, ethylenediamine (EDA), as both a base catalyst and nitrogen precursor, is introduced into Stöber-silica/carbon assembly system for the first time. Moreover, carbon materials with different nanostructures, including yolk-shell mesoporous carbon spheres (YSMCSs) and hollow mesoporous carbon spheres (HMCSs), are obtained by changing the amount of EDA. The resultant carbon nanospheres possess high surface areas (up to 2001 m 2 g -1 ), large pore volumes (up to 1.86 cm 3 g -1 ) and uniform mesopore size (∼2.6 nm for N-YSMCSs, ∼2.4 nm for N-HMCSs). The obtained two kinds of carbon spheres manifest excellent supercapacitors performance with high capacitance, favorable capacitance retention, and unprecedented cycling stability, which may be contributed to the hollow large surface area, high porosity, mesoporous structures, and N heteroatomic functionality. We believe that such structure integrations are useful for a lot of applications, such as advanced energy storage materials and catalyst supports.Recently, a Stöber-silica/carbon assembly (SSCA) route by using silica and surfactant as structure-assistant agent was developed, which has been an extraordinarily efficient way for structure regulation of carbon spheres. [30][31][32][33][34][35][36][37] Typically, Fuertes et al. developed a one-step route to produce core-shell silica@RF spheres by combing Stöber-silica and carbon process for the first time. [35] Carbonization was followed by etching of the silica in the silica/carbon composite, resulting in the formation of hollow carbon spheres. Except that, a silica assisted synthetic strategy was first established by Jaroniec et al., [36] which further enriched the SSCA

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