High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory-Huggins interaction parameter was found to be x(12) = -1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. The Lauritzen-Hoffman analysis was tested. The values of nucleation constant K(g) did not show any substantial variation. The non-isothermal crystallization of the blends was also tested. It was found that the crystallization is retarded in the case of blends, compared to the neat PESeb. (C) 2011 Elsevier Ltd. All rights reserved.