A new polymer-nanoclay hybrid based on polyvinyl acetate (PVAc)-organically modified montmorillonite (OMMT) has been developed via emulsion polymerization technique. By establishing the swollen capacity of Na montmorillonite and an organically modified montmotillonite with vinyl acetate (VAc), we deduced that compatibility between partners is related to hydrophobic interaction depending on monomer and montmorillonite hydrophobic nature. The hybrid materials were synthesized by one-step emulsion polymerization of VAc in the presence of OMMT using polyvinyl alcohol (PVA) as stabilizing agent. Conversions of VAc are not significantly affected by the OMMT load in the polymerization system. The maximal reaction rates were also evaluated. APV-OMMT hybrids were prepared via solution intercalation to be compared with PVAc-OMMT hybrids obtained by emulsion polymerization using PVA. TGA and XRD analyses were performed firstly to evaluate the hybrids, and also the TEM for morphological determination, and structure confirmation.