[en] Commercially available poly(propylene)imine (DAB-Am-32 and DAB-Am-64) dendrimers were used as single-molecule templates to tailor the porosity of silicas via a nonacidic sol-gel method. X-ray diffraction on both the as-prepared (oven-dried at 373 K) and the calcined (833 K) materials revealed that modest contraction took place on template removal and that the cavities created did not achieve three-dimensional ordering under the current synthesis conditions. Transmission electron microscopy of ''Pt-stained'' samples supported this picture. A modified Horvath-Kawazoe analysis of the argon adsorption isotherms indicated that DAB-Am-64 is a much more effective template than DAB-Am-32. Pyrolysis and oxidation protocols for template removal are also presented. (c) 2000 Materials Research Society