A series of lithium electrolyte materials based on hybrid of semi Inter penetrating Polymer Network of [poly(ethylene glycol)-polyurethane-polymethylmethacrylate] [60:40] and TiO2 nanofibers is described. TiO2 nanofibers are made by simple solvothermal procedure. Rutile phase of TiO2 and its fibrous morphology are confirmed by X-ray diffraction pattern and scanning electron microscopy image respectively. Semi Inter penetrating Polymer Network of polyethylene glycol-polyurethane/polymethylmethacrylate with LiClO4 and its nanocomposite with different weight percent of TiO2 nano fibers have been synthesized. The formation of Inter penetrating Polymer Network and its amorphous nature are confirmed by Fourier transform infrared spectra, X-ray diffraction pattern and differential scanning calorimetry results. Thermo gravimetric analysis shows enhanced thermal stability of the composite compared to the semi Inter penetrating Polymer Network system. The electrical characterizations of the nanocomposites are done by current–voltage (I–V) measurements and impedance spectroscopy. These results confirm that incorporation of TiO2 nanofibers by 18% enhances the conductivity of the Inter penetrating Polymer Network system by ten times. The nanoscale structure of the inorganic material is found to be responsible for the bulk properties of the system, especially those that differ from the properties of similar, pure salt-in-polymer electrolytes. Further differential scanning calorimetry, scanning electron microscopy and impedance data confirm the presence of two polymeric phases in the semi Inter penetrating Polymer Network. Power law exponents of individual phase of that semi Inter penetrating Polymer Network obtained by simulated fitting of the conductivity versus log frequency profile using universal power law reveals that cationic hopping in the polymethylmethacrylate phase and anionic hopping in the polyethylene glycol-polyurethane phase contribute significantly to the charge transport processes in these semi Inter penetrating Polymer Network.