Syndiotactic poly(vinyl alcohol) (PVA)/poly(vinyl pivalate/vinyl acetate) (P(VPi/VAc)) and atactic PVA/PVAc micro- and nanoparticles with skin/core structure have been prepared by heterogeneous saponification of P(VPi/VAc) and PVAc micro- and nanoparticles. Especially, to prepare P(VPi/VAc) and PVAc microparticles having various particle sizes and uniform particle size distribution, vinyl pivalate (VPi)/vinyl acetate (VAc) and VAc were suspension-polymerized using a low-temperature initiator, 2,2’-azobis(2,4-dimethylvaleronitrile). P(VPi/VAc) particles are promising precursor of stereoregular PVA embolic materials which can be introduced through catheters in the management of gastrointestinal bleeders, arteriovenous malformations, hemangiomas, and traumatic rupture of blood vessels. Monodisperse and/or nearly monodisperse P(VPi/VAc) and PVAc microparticles with various particle diameters were obtained by controlling suspension polymerization conditions. Monodisperse P(VPi/VAc) and PVAc microparticles having various particle sizes were partially saponified in the heterogeneous system. PVA/P(VPi/VAc) and PVA/PVAc microparticles having various tacticity and degree of saponification were produced by controlling various polymerization and saponification conditions. The coating of stereoregular PVA micro- and nanoparticles for drug release experiments was conducted with the strepo-avidin-alkaline phosphatase conjugate in variable conditions of pH value, coating buffer, and reaction temperature. Protein-coated syndiotactic PVA micro- and nanoparticles, which does not crosslinking, were more superior to controllability of drug release, durability, and dimensional stability to water and blood than atactic one.