The influence of poly(dicyclohexylitaconate) (PDCHI) content, on the crystallization kinetics, thermal properties, and hydrolytic degradation of poly(hydroxybutyrate-co-hydroxyvalerate), PHBV, was studied. Irrespective of the blend composition, the calorimetric and FTIR spectroscopy analyses indicate that the blend components are immiscible. The kinetics of non-isothermal crystallization and melting behavior of PHBV were studied by differential scanning calorimetry (DSC) and examined using non-isothermal Avrami and Mo's analyses. Based on Mo's model, the PDCHI content has significant effect on the crystallization kinetics of PHBV matrix. Despite the immiscibility of these polymers, the amorphous polyvinyl ester could extensively control the rate of hydrolytic degradation.