In this study the PANI/PHBV blends were prepared and thermal properties, crystallization behavior, microstructure of the blends were investigated. The PANI/PHBV blends were prepared by dissolution of PANI (emeraldine base doped with dodecylbenzenesulphonic acid, DBSA) and PHBV in chloroform and films were obtained by casting. PANI amount in the blend was varied from 0.1 to 1% wt. PANI/PHBV blends were characterized by FTIR spectroscopy and the thermal behavior were analyzed by differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). FTIR spectra of the pure PHBV and PANI/PHBV blend had similar peaks. However, blends spectra show an enlargement of bands, due interaction of the chain PANI with PHBV matrix. The crystallization behaviors were investigated using DSC, with at a scanning rate of 10oCmin−1. Curve of pure PHBV showed two melting peaks (159.1°C and 172.3°C). With the increase of PANI amount in the PHBV matrix, both of the melting peaks became wider and shifted to lower temperatures. The decrease trend of first and second melting points with increase of PANI amount, suggests a reduction in the crystallinity of the blends.