Poly(vinylidene fluoride) (PVDF) polymers are utilized in the processing of foods and beverages due to their highly stable nature. This makes plasticizer selection crucial. The incorporation of epoxidized oleic acid (EOA) as a bio-plasticizer into PVDF in the solution blending process was investigated. Scanning electron microscopy analysis showed the toughening effects in the structure of the blends. The degree of crystallinity was found to decrease with an increase in the EOA ratio. The melting temperature slightly decreased with the addition of EOA. A reduction was observed in the glass transition temperature (T_g), which was the effect of the plasticizer. Bio-plasticized PVDF exhibited increased thermal resistance with higher char formation. The scanning electron fractograph showed that EOA disrupted the PVDF crystallinity with a rise in amorphicity. Crystal formation was found to be in one dimension and dependent on the bio-plasticizer content. Hence, EOA has an excellent potential as a renewable resource to substitute for conventional petroleum-based plasticizers.