Poly(butylene terephthalate) (PBT)/polycarbonate (PC) samples, prepared via reactive blending in the presence of Ti- and Sm-based catalysts, resulted in block copolymers whose block length decreased as the mixing time increased. A single homogeneous amorphous phase occurred when the blocks had monomeric sequences shorter than 10 units. Otherwise, a crystalline phase of PBT developed. Also, in poly(ethylene terephthalate) (PET)/PC blends previously studied, the miscibility was strictly correlated with the crystallizability of the system. Therefore, the miscibility of the PBT/PC and PET/PC blends was compared with respect to the tendency of the PBT and PET blocks to crystallize under isothermal conditions. The crystallization rate of the PBT/PC copolymers was faster than that of the PET/PC copolymers with similar block lengths. Accordingly, the minimum crystallizable sequence length of the PBT blocks was shorter than that of the PET blocks (18 vs 31 monomeric unit sequences). This behavior was interpreted as an effect of the more flexible PBT units, which had a greater tendency to fold and crystallize than the PET units. Therefore, PBT, the blocks of which tended to crystallize even if they were very short and phase-separated, was characterized by a poorer compatibility with PC than that of PET. As a result, the block size had a fundamental role in determining the crystallizability and, therefore, phase behavior of the semicrystalline block copolymers. (C) 2004 Wiley Periodicals, Inc.