Nanocapsules with an oily core and an organic/inorganic hybrid shell were elaborated by miniemulsion (co)polymerization of styrene, divinylbenzene, -methacryloyloxy propyl trimethoxysilane and N-isopropyl acrylamide. The hybrid copolymer shell membrane was formed by polymerization-induced phase separation at the interface of the oily nanodroplets with water. It was shown that the size, size distribution and colloidal stability of the miniemulsion droplets were extremely dependent on the nature of the oil phase, the monomer content and the surfactant concentration. The less water-soluble the hydrocarbon template and the higher the monomer content, the better the droplet stability. The successful formation of nanocapsules with the targeted core-shell morphology (i.e., a liquid core surrounded by a solid shell) was evidenced by cryogenic transmission electron microscopy. Both nanocapsules and nanoparticles were produced by polymerization of the miniemulsion droplets. The proportion of nanoparticles increased with increasing monomer concentration in the oil phase. These undesirable nanoparticles were presumably formed by homogeneous nucleation as we showed that micellar nucleation could be neglected under our experimental conditions even for high surfactant concentrations. The introduction of -methacryloyloxy propyl trimethoxysilane was considered to be the main reason for homogeneous nucleation.