The electrochemical, X-ray diffraction, thermal, rheological and spectroscopic studies have been carried out to examine the effect of nanosized TiO2 addition in different concentration to polymethylmethacrylate (PMMA) based gel polymer electrolytes (GPE). This work demonstrates that with optimum concentration of TiO2 loadings in GPE, the ionic conductivity enhances with negligible effect on other electrochemical properties. The obtained ionic conductivity value is >10−3 Scm−1. An increase in viscosity by an order of magnitude is obtained which also restricts the flow property of GPE. The addition of TiO2 retains the amorphicity of the GPE while the T g increases. Enhanced mechanical stability of these composite polymer electrolytes (CPEs) with solid-like behavior is evident from their appearance. The activation energy has been calculated by fitting the conductivity profile in VTF equation, which decreases on the addition of fillers. FTIR characterization also confirms the interaction of filler with CO of PMMA. The capabilities and properties exhibited by these CPEs will be of immense interest for electrochemists to use them in solid-state devices.