Titanium oxide (TiO2) nanoparticles were fabricated by using the sol–gel tech- nique. By controlling the calcination temperature, the different structures of TiO2 (anatase and rutile) have been achieved which is considered a new tech- nique for phase transformation. Moreover, PVA (polyvinyl alcohol)/TiO2 nanocomposite with various TiO2 phases was accomplished by room temper- ature casting method. The microstructure of TiO2 nanoparticles and its effect on the PVA amorphous phase was confirmed by X-ray diffraction (XRD) and scanning electron microscope (SEM). The functional groups of PVA and TiO2 were inspected by Fourier transform infrared spectroscopy (FT-IR). SEM exhi- bits an agglomeration nature of TiO2 nanoparticles through the PVA matrix. In this study, the dc conductivity, as well as the transport properties such as activation energy, ions number in unit volume, hopping distance, and polaron’s radius were discussed. In the light-temperature of the polaronic hopping con- duction models, the electrical conductivity data were examined which is well- described by polaronic models. Besides, it is noted that the nonadiabatic small polaron hopping conduction is realized in this system. The density of state and the decay constant values are acceptable for the localized states.