Herein, we report for the first time the successful preparation of thiometallate-based precursors for use in a bottom-up synthetic process of supported Pt and PtNi nanoparticle catalyst. This precursor enabled the monodisperse synthesis of supported Pt nanoparticles and the in situ formation of S, which were caught directly in a collection system by the nanoparticle synthetic processes consisting of impregnation and thermal processes. S is proven to act as a capping agent in generating highly stable nanoparticles with the size ranging from 2 nm to 3 nm and further favors the formation of monodispersed particles by solid-state digestive ripening. The proposed synthetic methodology can be applied to high-quality PtNi alloy nanoparticle systems. The current route is readily scalable, and multi-gram quantities can be prepared. The prepared carbon-supported Pt and PtNi nanoparticles were characterized as electrocatalysts for the oxygen reduction reaction and exhibited superior performance and durability to commercial Pt/C.