Poly(vinyl alcohol) (PVOH) can be advantageously used in miniemulsion polymerization as it yields latexes more stable than those produced by conventional emulsion polymerization. Latex stabilization and properties are affected by the extent of grafting of PVOH. The effect of the initiator system and the polymerization process (miniemulsion vs conventional emulsion polymerization) on the extent of grafting of PVOH in the polymerization of vinyl acetate and Veova10 was studied. It was found that the fate of the PVOH was strongly influenced by the initiator system and the process employed. The use of potassium persulfate in miniemulsion polymerization led to the maximum grafting level. The mechanistic reasons of these results were discussed.