© The Royal Society of Chemistry 2016. Multifunctional porous nanospheres are desirable for many applications, but their synthesis involves multi-step procedures and their simplification still remains a challenge. Herein, we demonstrate a facile synthesis of polymer-silica nanospheres by using an extended Stöber method via triconstituent co-assembly of 3-aminophenol, formaldehyde, and bis[3-(triethoxysilyl)propyl]tetrasulfide followed by copolymerization. N,S-doped carbon-silica nanospheres with either smooth or rough surface can be obtained by direct carbonization of the polymer-silica nanospheres. The carbon-silica spheres feature multifunctional properties and exhibit very good performance as adsorbents for CO2 capture (67 cm3 g-1 at 0 ± 1 °C and 1.0 bar) and as supercapacitor electrodes with high specific capacitance (221 F g-1). This strategy could pave the way for design of carbon nanostructures at molecular level for multi-purpose applications.