Nitrogen-doped hollow carbon spheres (NHCSs) are well prepared by using Cu₂O microspheres as a hard template and 3-aminophenol formaldehyde resin polymer as carbon and nitrogen precursors. The thickness of the carbon shell can be easily controlled in the range of 15–84 nm by simply adjusting the weight ratios of the precursors to Cu₂O microspheres, and the Cu₂O templates can also be further reused. Physicochemical characterization demonstrates that the obtained NHCSs possess a well-developed hollow spherical structure, thin carbon shell and high nitrogen doping content. Due to these characteristics, when further utilized as electrodes for supercapacitors, the NHCSs with the carbon shell thickness of 15 nm show a high capacitance of 263.6 F g⁻¹ at 0.5 A g⁻¹, an outstanding rate performance of 122 F g⁻¹ at 20 A g⁻¹ and an excellent long-term cycling stability with only 9.8% loss after 1000 cycles at 5 A g⁻¹ in 6 M KOH aqueous electrolyte. This finding may push forward the development of carbon materials, exhibiting huge potential for electrochemical energy storage applications.