Hollow carbon spheres (HCSs) are prepared using poly(ionic liquids) (PILs) as a carbon precursor and monodisperse silica particles as a template for the first time. The ILs form a uniform polymer coating on the template surface after polymerization. Carbonization of the coating and the subsequent removal of the template produces porous carbon spheres with a hollow structure. The HCSs possess a high surface area, good conductivity, and porosity suitable for mass transport, and they can be used as a support for Pt electrocatalysts. Pt nanoparticles with an average size of 2.8 nm are homogeneously distributed onto the HCSs. The high surface area and unique structure facilitates the fine dispersion of Pt nanoparticles. The obtained Pt/HCSs exhibit a significant catalytic activity for the oxidation of methanol. (C) 2011 Elsevier B.V. All rights reserved.