Thin films of Nano-Composite Polymer Electrolyte (NCPE) consisting of poly (vinyl alcohol) (PVA), ortho phosphoric acid (H3PO4), and Al2O3 nanoparticles (size ~50 nm) have been prepared by solution cast technique. Solid Polymer Electrolytes (SPE) (PVA-H3PO4: 70:30 wt%) as first phase host matrix and nanoparticles of Al2O3 as second phase dispersed in different wt. ratios are utilized for the preparation of thin films of NCPE. The DSC result shows that both glass transition and melting temperatures of SPE films decreases with addition of Al2O3 nanoparticles. The FTIR spectra give indication about possible interactions between host matrix and dopants for its complexation. It has been found that ionic conductivity (σ = 2.7 x 10-4 S/cm) of the NCPE film having 2 wt% of nanoparticles is enhanced by one order of magnitude over the conventional SPE system at room temperature. The ionic transport behaviors in both SPE and NCPE films have been characterized and compared in terms of ionic conductivity (σ) and ionic transference number (tion) responsible for ionic conduction. The temperature dependent conductivity behavior has been used to compute the activation energy (Ea) involved in the conduction process.