Blend films based on PEO/PVA (50/50 wt%) undoped and doped with different concentration of TiO2 nanoparticles are prepared by casting technique. Characteristic properties of the blend films are investigated using Fourier transform infrared, X-ray diffraction (XRD), ultraviolet–visible spectra (UV-Vis), scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis. On the basis of results obtained from IR and DSC data, blends appear to be immiscible. XRD, UV-Vis and TG reveal that 1.0 wt% TiO2 is most ordered concentration. SEM reveals that the presence of TiO2 leads to changes in the surface morphology and gives rise to crystalline domains with coarse spherulitic structure. It has been seen that spherulites increases with addition of TiO2 nanoparticles. TG studies conclude that this concentration has low E*, ΔS* and ΔH*. So, it is more ordering and has low thermal motion. Kinetic thermodynamic parameters such as activation energy, enthalpy, entropy and Gibb’s free energy are evaluated from TG data using Coat’s–Redfern model.