Pure and different concentrations of Mn 2+ (1.0, 2.0, 3.0, 4.0 and 5.0 mol%) doped PVA/MAA:EA polymer blend films were prepared by solution casting method. The structural analysis of the prepared samples by X-ray Diffraction reveals broadening of diffraction peak which implies a lower degree of crystallinity with higher Mn 2+ concentration. UV-Vis spectral analysis shows a significant red shift in the optical band gap with increase in Mn 2+ concentration. FTIR spectrum exhibits bands characteristic of stretching and bending vibrations O-H, C-H, C=C and C-O groups and the changes in the FTIR spectrum with dopant concentration indicate the complexation of dopant with the polymer blend. The conductivity study shows that the doping of Mn 2+ ions into the polymer blend system enhances its ionic conductivity from 2.46 X 10 -8 Scm -1 for pure film to 1.41 X 10 -7 Scm -1 for 5 mol% of Mn 2+ ions at room temperature, which is due to the increase in mobile charge carriers and their increased mobility which is explained in terms of an increase in the amorphicity.