Ferroelectric films have been widely studied for their energy harvesting applications and flexible ferroelectric films for their piezoelectric energy harvesting. In this work, we explore tuning the PVDF/BaTiO3 composite flexible films for pyroelectric energy conversion applications. This work reports the influence of barium titanate particles (BaTiO3) in the formation of β-phase polyvinylidene fluoride (PVDF) on PVDF/BaTiO3 composite films based on Fourier transform infrared and Raman spectroscopic studies. PVDF/BaTiO3 composite films with different weight percentages of BaTiO3 were prepared by spin coating technique. Fourier transform infrared spectroscopy and Raman spectroscopic analysis of PVDF/BaTiO3 composite films indicated that the polar β-phase of PVDF nucleated by the incorporation of BaTiO3 through CF2 interaction with BaTiO3 particles as inferred from the filler percentage dependence study of vibration modes. The 15 wt% concentration of PVDF with 5 wt% of BaTiO3 composite film has higher β-phase content and better crystallinity. The improved film quality, in turn, enhances the pyroelectric coefficient and pyroelectric energy conversion figure of merit.