Spherical poly(ionic liquid) (PIL) nanoparticles of different size (25-70 nm) were synthesized and applied as a novel colloidal soft template for the preparation of meso- and macroporous inorganics, here exemplified with silica and its metal nanoparticle doping via nanocasting. Pore size and pore architecture can be adjusted by appropriate choice of the template and the reaction conditions. Unexpectedly, it was found that the in situ generated methanol plays a very important role during the casting process. It enlarged the overall surface area by introducing a significant fraction of micropores and small mesopores. The largest specific surface area was obtained at an optimized ratio of tetramethyl orthosilicate (TMOS) to PIL nanoparticle. In addition, PIL nanoparticles pre-functionalized with Pt metal nanoparticles were used in the same manner as hybrid templates for nanocasting. The pyrolysis conditions were optimized to synthesize mesoporous silica functionalized with uniformly distributed metal nanoparticles of very small size in a one-pot process. (C) 2013 Elsevier Ltd. All rights reserved.