Poly(vinyl alcohol) is often used in vinyl acetate emulsion polymerization as a protective colloid, but its role is complex and controversial since it partakes in grafting reactions with the monomer, influencing process mechanisms, and affecting the colloidal properties of the latex. Furthermore, in industrial operations, the wide scatter of macromolecular properties of the commercial types of poly(vinyl alcohol) causes process irreproducibilities. In this work different types of polyvinyl alcohol were used to perform a series of polymerizations, and their kinetics were compared. A selective solubilization procedure was applied to separate the three fractions of poly(vinyl alcohol) in the final latex: free in the water phase, physically adsorbed onto the polymer particles and chemically grafted. These results were compared with those obtained from pure adsorption measurements of polyvinyl alcohol onto 'emulsifier-free' polyvinyl acetate dispersions. The theological behavior of the different latexes was also compared, and the results were used to formulate an hypothesis on the interaction mechanisms acting in these systems. (C) 2004 Elsevier Ltd. All rights reserved.