Hybrid particles consisting of an organic polymer and silica or polyorganosiloxanes are interesting building blocks for nanocomposites. The synthesis of such particles typically requires multiple reaction steps involving the formation of polymer colloids and the subsequent deposition of silicon-containing material either inside or on the surface of these colloids, or vice versa. In 2014, we reported a facile method for the one-pot synthesis of sub-micron sized hybrid particles based on simultaneous sol-gel conversion of organotrimethoxysilanes and emulsion polymerization of a vinylic monomer, illustrated by the synthesis of polystyrene-polyphenylsiloxane particles from the monomers styrene and phenyltrimethoxysilane (Segers et al (2014). In this process, the required surface active species was formed in situ through hydrolytic conversion of phenyltrimethoxysilane to phenylsilanolate oligomers. Introduction of thiol groups in such hybrid particles should yield particles suited for functionalization with small metal nanoparticles, e.g., Au. Here, we present the synthesis of thiol-containing hybrid particles consisting of poly(3-mercaptopropyl)siloxane and polystyrene using the one-pot synthesis method based on simultaneous conversion of (3-mercaptopropyl)trimethoxysilane and styrene. We prepared particles from different volume ratios of (3-mercaptopropyl)trimethoxysilane and styrene, ranging from 1:99 to 80:20. The resulting spherical hybrid particles displayed different sizes, compositions, and architectures (including core-shell), which were studied in detail using scanning electron microscopy, thermogravimetric analysis, and scanning transmission electron microscopy combined with energy dispersive x-ray spectroscopy. The composition of these particles, and consequently the number of thiol groups available for further functionalization such as metal anchoring, was tunable.