Polyvinyl alcohol (PVA) /Poly (tetrafluoroethylene) (PTFE)/Titanium oxide (TiO2) was prepared by ( 5, 10 and 15 wt %) TiO2 loading. The miscibility, thermal property and microstructure of the composites were characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The electrical relaxation dynamics including dielectric and electrical conductivity was examined as a function broadband of frequency and temperature. The dielectric data was analyzed via the electric modulus. The Maxwell-Wagner-Siller (MWS) effect corresponds to interfacial polarization at low frequency follows Arrhenius behavior. The α-mode relaxation is attributed to glass-rubbery transition in composites, obeys the Vogel- Taman-Fulcher (VTF) model. A slight bump was noted at relatively high temperature and high frequencies termed as Intermediate dipolar effect (IDE) obeys the Arrhenius behavior. Conductive mechanism was analyzed via AC conductivity spectra. However, DC conductivity follows Arrhenius equation. The overall studies confirm that the self relaxation mechanism of PVA/PTFE composites were modified by TiO2, offers the tuning conductivity as a function of the temperature which can be used in various electronic applications.