Novel model block copolymers of (R,S)-beta-butyrolactone with pivalolactone (PVL) are prepared in order to define the effect of crystalline domains provided by poly(pivalolactone) on the biodegradability of atactic poly(beta-butyrolactone), a-PHB. The "living" a-PHB is synthesized from racemic beta-butyrolactone, in the presence of potassium alkoxide/18-crown-6 complex, and such a living polymer is applied for polymerization of PVL, yielding block copolymers, a-PHB-b-PPVL, of tailored molecular weight and composition. The copolymers contain an amorphous phase with T-g = 5 degrees C, associated with the a-PHB block, and a high melting crystalline phase, whose amount increases with PPVL content. Films of copolymers containing 9 (PVL9), 17 (PVL17), and 23 mol % of PPVL (PVL23) are exposed to PHB-depolymerase A from Pseudomonas lemoignei (37 degrees C, Tris-HCl buffer pH = 8). While plain a-PHB does not biodegrade, the biodegradation rate of a-PHB-b-PPVL copolymers increases (PVL9 much less than PVL17 < PVL23) along with the increase of crystalline PPVL domains. The biodegradation rate of PVL23 is similar to that of natural (crystalline) PHB. On the basis of a comparison of a-PHB-b-PPVL composition changes (by H-1 NMR) with weight loss during biodegradation experiments, it is concluded that in the copolymers studied only the a-PHB block is attacked by the enzyme and that the crystalline block of nonbiodegradable PPVL efficiently promotes enzymatic attack to a-PHB, by providing a binding support to the enzyme.