Abstract Nanogel (hydrophilic polymer nanoparticles) core–silica shell nanoparticles were successfully fabricated via hydrolysis and condensation reaction of tetraethoxysilane (TEOS). Transition-metal tetrafluoroborate-containing nanogels were used as templates for fabrication in inverse systems (cyclohexane as continuous phase). Magnetic, hollow silica particles were subsequently formed by removing the polymer core and converting iron salts to iron oxides via heat treatment. We propose that the formation of the core–shell morphology is induced by the promoted precipitation of silica species at the surface of nanogels due to the interaction between silica species and transition-metal tetrafluoroborate. The influence of the synthesis parameters (type and amount of salts, pH of the nanogels, and amount of TEOS) on the particle morphology was systematically investigated. The pore properties and specific surface area of the hollow silica particles could be modified by the varying the amount of salt.