The potential application of Pisolithus arhizus fungi as an effective sensitizer in bio-sensitized solar cells (BSSCs) is the first of its kind to investigate the photovoltaic performance of BSSCs in polar protic and aprotic solvents. The soxhlet extraction method was employed to extract dye molecules in organic solvents including chloroform, 2-propanol, acetone, ethanol, methanol and DMSO and named PA1, PA2, PA3, PA4, PA5, PA6 to fabricate BSSCs. TiO2 and Platinum were used as working and counter electrodes. The structural, optical, morphological properties of the extracted dyes and dye anchored TiO2 films were analyzed through FTIR, UV–Vis spectroscopy and FESEM analysis. The optical absorption analysis revealed the presence of pisoquinone pigments in the fungi, from flavonoid family. The current-voltage, electrochemical impedance and cyclic voltammetry analysis showed that the PA4 ethanolic-based BSSC demonstrated the highest power conversion efficiency of 1.31 % compared to other DSSCs, with a Jsc of 3.40 mA cm−2 and Voc of 514 mV and the bandgap energy of 1.8eV. The order of the conversion efficiency for DSSCs with different solvents was ethanol (PA4) > methanol (PA5) > acetone (PA3) > DMSO (PA6) > 2-propanol (PA2) > chloroform (PA1). This finding highlights that selecting optimal, novel sensitizers and extraction solvents is crucial to maximize solar cell efficiency.