In this study, we attempted to prepare a binary polymer blend of poly (vinylidene fluoride) (PVDF) and poly lactic acid (PLA) by employing solvent casting method. Both PVDF and PLA possessing good piezoelectric properties, are considered for energy storage and energy harvesting applications. PVDF-PLA blends were uniaxially stretched at stretch ratios 1–3 to modify the structural and dielectric properties. Spectroscopic studies such as; Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis confirmed the improvement in electroactive polar phases of PVDF thus revealing the successful intermolecular interaction between CH₂ and CF₂ group of PVDF and -C = O or −OH or −CH₃ group of PLA leading to good compatibility between both the polymers. Impedance specroscopy measurement confirmed the enhanced dielctric behaviour of unstretched (ε’ = 10.5 and tan δ = 0.001) as well as mechanically stretched blend (ε’ = 14.4 and tan δ = 0.001) which is ascribed to the formation of smaller spherulites at their interface which eventually facilitated their interfacial polarisation.