Biopolymers of polyhydroxyalkanoates (PHAs) are produced by pure bacterial strain of Alcaligenes eutrophus TISTR 1095 via batch fermentation using sugarcane juice as a carbon source, and yielded up to 21% (w/w) after recovery process. The PHAs are blended with bio-based materials such as tapioca and corn starch including glycerol and methanol to improve their microstructures. The combination of various plasticizers with PHAs is studied in different ratios. The PHAs and starch are mixed for 3% w/v and 30% w/v in hot chloroform, respectively. The varieties of PHAs to starch solution ratios are situated for casting as of films. The PHAs blended films are characterized by polarized light microscopy, differential scanning calorimetry (DSC) and x-ray diffractometry (XRD). The initial PHAs indicate remarkably crystalline structure with cross-polarized light on optical microscope. Macroscopic scales of their films are very brittle and flexible. However, their microscopic scales present small patches of particular components from each starch. Immiscibility of the blends is gradually increased on adding the starch portions. Additional glycerol shows more strongly interfacial adhesion between starch and PHAs, and methanol produces specifically thin films. Melting transition temperatures of blended films are slightly higher than the biosynthesized PHAs as examined by DSC. Corn starch mixture causes highly brittle films than tapioca mixtures, which indicates poor adhesion between corn starch and the PHAs. This result is correspondent to their highly crystallinity from diffractogram. Microstructural evolution of the blended films is increased slightly crystallinity by the solution casting.