Poly(vinyl alcohol)/montmorillonite/silver hybrid nanoparticles are successfully fabricated by one-step electrospraying process in aqueous solution. The aim of this project is to design an optimum solution parameter for electrospraying system and evaluate inorganic material effects to antibacterial performance and thermal properties. Hybrid nanoparticles could be obtained at low molecular weight and concentration of the polymer. Transmission electron microscopy analysis showed montmorillonite and silver were well dispersed in poly(vinyl alcohol) nanoparticles and enhanced thermal properties of the composite material. In anti-bacterial test, the poly(vinyl alcohol)/montmorillonite/silver hybrid nanoparticles showed an excellent anti-bacterial performance.