This study includes the successful fabrication of polyvinylidene fluoride (PVDF) based hybrid nanocomposite films loaded with nickel oxide (NiO) and barium titanate (BaTiO3) fillers via simple sol–gel casting techniques to optimize the crystallinity and β-phase formation for various sensor applications. A systematic study has been performed to assess the effect of fillers (NiO and BaTiO3) on the crystal structure, morphology and electrical conduction properties of PVDF–NiO–BaTiO3 hybrid nanocomposite films using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM) using energy dispersive spectroscopy and current–voltage (I–V) measurement techniques. XRD and FTIR results indicate that the incorporation of nanostructured fillers NiO and BaTiO3 leads to the formation of long stabilized planar zigzag and all-trans conformation (TTTT) inducing the growth of electroactive β-phase and crystallinity. XRD results show that the degree of crystallinity reaches a maximum value of 85% for incorporation of 2.5 wt% of NiO and 27.5 wt% of BaTiO3. FTIR results show 85% of electroactive β-phase growth achieved by incorporating 7.5 wt% of NiO and 22.5 wt% of BaTiO3. FESEM micrographs of hybrid films show that both NiO and BaTiO3 particles are well dispersed within the PVDF pattern with the porous surface resulting in enhanced electrical conductivity. Current–voltage (I–V) measurement shows the charge transport process in PVDF composites loaded with NiO and BaTiO3 fillers is mainly governed by Richardson Schottky emission. The significant increase in the electrical conductivity of PVDF–NiO–BaTiO3 hybrid nanocomposite opens a new window for possible use in miniaturization of electronics and energy harvesting devices.