Gel polymer electrolytes (GPEs) consisting of poly(1-vinylpyrrolidone-co-vinyl acetate) P(VP-co-VAc) with the different tetrapropylammonium iodide (TPAI) salt concentration are prepared. The dielectric and electric dispersion behaviors of the GPEs are studied by dielectric relaxation spectroscopy at room temperature. The dielectric studies imply that dielectric constant (ε′) and dielectric loss (ε″) values decrease with increase in frequency at lower frequency region whereas frequency independent behavior is observed in the high frequency region. The trend of the dispersion part of the electric modulus shows a shift towards higher region of frequency indicating shorter relaxation time with an increase in TPAI concentration. The GPE samples were observed to obey Arrhenius behavior and the highest ionic conductivity obtained is 1.60 × 10−3 S cm−1 at room temperature. The GPE samples are then fabricated into dye sensitized solar cells for photovoltaic studies. Highest efficiency of 3.07% is obtained with short circuit current density of 6.86 mA cm−2, open circuit voltage of 727 mV and fill factor of 62%