The energy storage capacity of porous carbon materials is closely tied to their surface structure and chemical properties. However, developing an innovative and straightforward approach to synthesize yolk-shell carbon spheres (YCs) remains a great challenge till date. Herein, we prepared a series of porous nitrogen-doped yolk-shell carbon spheres (NYCs) via a “pyrolysis-capture” method. This method involves coating the resorcinol–formaldehyde (RF) resin sphere with a layer of compact silica shell induced by 2-methylimidazole (ME) catalysis to produce a confined nano-space. Based on the confined effect of compact silica shell, volatile gases emitted from the RF resin and ME during pyrolysis can not only diffuse into the pores of the RF resin but can also be captured to form an outer carbon shell. This results in the tunable structures of NYCs materials. As the pyrolysis temperature rises, the shell thickness of NYCs reduces, the pore size expands, the roughness increases, and the N/O content of surface elements is enhanced. Notably, as an electrode material used forsupercapacitors,the optimized NYCs-800 exhibits excellent performance with a capacitance of 301.2F g−1 at the current density of 1 A/g and outstanding cycling life stability of 96.1% after 10,000 cycles. These results signify that controlling the surface structure and chemical properties of NYCs materials is an effective approach for constructing advanced energy storage materials.