To prepare high molecular weight (HMW) poly(vinyl acetate) (PVAc) with high yield and high linearity as a precursor of HMW poly(vinyl alcohol) (PVA), vinyl acetate (VAc) was emulsion polymerized using, azo initiator, 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH). This was compared with the polymerization using potassium peroxodisulfate (KPS) as an initiator at various polymerization conditions. PVA, having a maximum number average degree of polymerization (P-n of 3500 was obtained by the saponification of PVAc with P-n of 13,000-14,000, degree of branching (DB) for the acetyl group of about 3.4-3.5, and a maximum conversion of VAc into PVAc of 95%, which was polymerized by AAPH. These numerical values were superior compared with 14,500-15,000 of P-n of PVAc, obtained by KPS, and 3100 of maximum P-n of resulting PVA, DB of about 3.7-3.8, and maximum conversion of 90%. From the foregoing experimental results, we found that AAPH was a more efficient initiator than KPS in increasing both conversion of PVAc and molecular weight of PVA. In addition, PVAc microspheres, obtained by these emulsion polymerizations, can be converted to PVA / PVAc shell / core microspheres through a series of surface-saponifications, maintaining their spherical morphology. Various surface morphologies, such as flat or wrinkled and swellable or nonswellable ones formed by the various molecular parameters and saponification conditions, were examined. C 2004 Wiley Periodicals, Inc.