In this work, enhancement of ionic conductivity and long-term stability through the addition of diphenylamine (DPA) in poly(ethylene oxide) (PEO) is demonstrated. Potassium iodide (KI) is adopted as the crystal growth inhibitor, and DPA is used as a charge transport enhancer in the electrolyte. The modified electrolyte is used with titanium dioxide (TiO2) nanoparticles, which is systematically tuned to obtain high surface area. The dye-sensitized solar cell (DSSC) showed a photocurrent of 14 mAcm2 with a total conversion efficiency of 5.8% under one sun irradiation. DPA enhances the interaction of the TiO2 nanoparticle film and the I-/I3- electrolyte leading to high ionic conductivity (3.5 × 10-3 Scm-1), without compromising on the electrochemical and mechanical stability. Electrochemical impedance spectroscopy (EIS) studies show that electron transport and electron lifetime are enhanced in the DPA added electrolyte due to reduced sublimation of iodine. The most promising feature of the electrolyte is increased device stability with 89% of the overall efficiency preserved even after 40 days.