In this research, various concentrations of manganese dioxide (MnO2) is composed by polyvinyl alcohol (PVA) to forming PVA /MnO2 films. The XRD and SEM are respectively demonstrated the structure and morphological characteristics of the films. The XRD results show that the PVA/MnO2 films is fabricated successfully. The SEM results demonstrate that MnO2 is dispersed evenly along the PVA polymeric chains. The conductivity, impedance and energy density were measured via an LCR bridge with frequency 102 to 106 Hz. There is an increase in dielectric from 64 for PVA to 95 for PVA/0.06MnO2 at 105 Hz, and also the conductivity increases from 3.61x10-3 S/cm for PVA to 5.33x10-3 S/cm for PVA/0.06MnO2. The optical characteristics of PVA and PVA/MnO2 films were recorded by UV/Vis spectroscopy. The band gap reduced from 5.01 eV for PVA to 4.85, 4.71, 4.59 eV respectively for PVA/0.02MnO2, PVA/0.04MnO2, and PVA/0.06MnO2. And the Urbach tail is modified from 1.72 eV for PVA to 3.12, 3.453, and 3.66 eV respectively. The results of the present work open the possibility for applied in different devices as energy storage systems and optoelectronics.