The real part of the dielectric constant (ε′) of pure and doped polyvinyl alcohol (PVA) with 1, 2 and 3 wt% vanadate was measured as a function of temperature and frequency. (ε′) decreases with increasing frequency due to a rapid variation of the field accompanied with the applied frequency as well as the disordering of the segmental parts of the polymer chain. The vanadate effects appear in a form of increasing the crystallinity in the sample leading to a decrease in (ε′), except in the case of 2 wt% vanadate in which (ε′) is drastically increased. The d.c. conductivity for the vanadate doped PVA is measured as a function of temperature. The values of the activation energy as obtained from the experimental data give information about the presence of more than one conduction mechanism as well as the useful applications of PVA, especially in the field of electronics.