A novel method of introducing a Limonene obtained from orange fruit skin (Lim) is successfully incorporated in Poly (ethylene oxide) (PEO) with KI and I2 redox couple and employed in a dye‐sensitized solar cell (DSSC). Scanning electron microscopy (SEM), X‐ ray diffraction (XRD) Ultra violet‐visible spectrum (UV‐Visible), Fourier transform infrared spectrum (FTIR), Thermo gravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS) studies described the influence of Lim on ionic conductivity and the photovoltaic properties of the PEO/KI/I2 system. The temperature‐dependent conduction mechanism of ionic motion and ionic interactions as a function of frequency has been studied. The dielectric behavior of the electrolyte samples were carried out over a wide frequency range (∼1 MHz to 20 Hz) at various temperatures. A DSSC system fabricated with the prepared PEO/KI/I2/Lim polymer electrolyte facilitating a fill factor of 0.52, a short‐circuit current density (Jsc) of 14.1 mAcm−2 and an open‐circuit voltage (Voc) of 795 mV yields the achieved solar to electrical energy conversion efficiency of 5.83 % under irradiation of 1 sun (100 mWcm−2). The compound Lim thus effectively enhanced the ionic conductivity of the composite polymer electrolyte and hence the photovoltaic performance of the fabricated DSSC.