Emulsion polymerizations of vinyl acetate (VAc) with polyvinyl alcohol (PVA) as emulsifier were carried out by both batch and semicontinuous processes. The extent of grafting of vinyl acetate onto the PVA chains was investigated by a new method for separating the various polymer fractions in high solids content latexes. The quantification was carried out by a three-step separation and selective solubilization of the PVAc latexes. After the separation, the water-soluble PVA and the solvent-soluble PVAc components were characterized by gel permeation chromatography and C-13-NMR, from which the accuracy of this method was verified.