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The thin film of nanocomposites was prepared by solution casting methods and characterized by UV–Vis spectra, Raman spectra and scanning electron microscopy (SEM). The optical band gap was determined by Tau plots. The band gap of PVDF was determined with and without BaZrO3 nanoparticles. It could be seen that the band gap decreases from 4.98 to 3.32 eV in the presence of BaZrO3 nanoparticles in PVDF matrix. The Raman study identifies the interacting species with PVDF due to structural change by the addition of BaZrO3 nanoparticles. This helps to understand the potential of new nanocomposites. The structural changes were analyzed by crystallinity, nature of bonds, phase transition from G to B-phase, etc. SEM images represent the change in spherulitic morphology of PVDF by incorporation of BaZrO3 nanoparticles. SEM images are presented the aggregation of BaZrO3 nanoparticles in PVDF matrix causes the generation of larger particles in PVDF chain. DSC supports the crystallization of PVDF nanocomposites upon heating due to the rearrangement of PVDF structure in the presence of BaZrO3 nanoparticles. It is observed that BaZrO3 nanoparticles enrich the structural, thermal and piezoelectric properties due to the change in spherulitic morphology, which creates a large number of micro- to nano-sized pores, increases the β-phase content of the PVDF. [ABSTRACT FROM AUTHOR]