Poly(vinyl acetate-co-vinyl alcohol) copolymers LP(VAc-co-VA)] were prepared by acidic hydrolysis of poly(vinyl acetate) (PVAc) at various reaction time, and the degree of hydrolysis was analyzed by C-13 nuclear magnetic resonance spectroscopy (NMR). Blends of poly(L-lactic acid) (PLA) and P(VAc-co-VA) were prepared by a solvent casting method using chloroform as a co-solvent. The PLA/PVAc blends exhibited a single glass transition over the entire composition range, indicating that the blends were miscible systems. On the contrary, for the blends with even 10% hydrolyzed PVAc copolymer, the phase separation and double glass transition were observed. With increasing neat PVAc contents, the heat of fusion decreased and the melting peaks shifted to lower temperature. The interaction parameter indicated negative values for up to 10% hydrolyzed samples, but positive values at more than 20% hydrolyzed one. Small angle X-ray scattering analysis revealed that the long period and the amorphous layer thickness increased with PVAc composition, suggesting that a considerable amount of PVAc component located in the interlamellar region. Polarized optical microscopy showed that the texture of spherulites became rougher on increasing the PVAc content. In the case of P(VAc-co-VA) copolymer, the intensity of polarized light decreased significantly, indicating that P(VAc-co-VA) component seemed to be expelled out of the interfibrillar regions. Scanning electron microscopy analysis revealed that the significant phase separation occurred with increasing the degree of hydrolysis. In the case of 70/30 blend of PLA and P(VAc-co-VA) with 30 mol% vinyl alcohol, the P(VAc-co-VA) copolymer formed the regular domains with a size of about 10 mum. (C) 2003 Elsevier Science Ltd. All rights reserved.