Vinyl functionalized silica spheres (VFSSs) are prepared by one-step reaction using the aqueous solution of organosilane. The synthetic method is effective and reproducible with one process used. The VFSSs could self-assemble into three-dimensional (3D) fcc photonic crystals. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that the VFSSs were highly monodisperse and their surfaces were sufficiently smooth. The size of the VFSSs could be controlled by adjusting the reaction temperature. The sphere size reached its minimum, 394 nm, around 45 degrees C and became larger when the temperature was either elevated or lowered. The maximum sphere size, 515 nm, was obtained around 15 degrees C. This work is expected to extend to the preparation and size control of other kinds of hybrid silica spheres. (C) 2011 Elsevier B. V. All rights reserved.