The carbonization and activation of nano-sized aluminosilicate resin (AlSiR) spheres with a diameter of about 500 nm were performed under various conditions. The carbonization of the AlSiR under H2O-vapor/N2 flow resulted in greater improvement of the physical properties of the shells on the carbon hollow spheres (CHSs) than that obtained under pure nitrogen flow. The water vapor activation of the carbonized AlSiR spheres was found to constitute a useful method as compared with the water vapor activation of the CHSs etched in HF solution; however, in order to increase the pore volume for a particular pore size of 4 nm, the latter method was more effective than the former method.