Dye-sensitized solar cells (DSSCs) offer a promising route for sustainable energy conversion, with natural photosensitizers emerging as attractive alternatives to conventional synthetic dyes due to their abundant resources, cost-effectiveness, and eco-friendly materials. However, the efficiency of DSSC utilizing natural photosensitizer remains low. In this study, we investigate the utilization of novel natural photosensitizers extracted from gambier leaves, gambier branches, cinnamon, and petiole of tectona leaves, which contain flavonoids/tannins, chlorophyll, and anthocyanins, aiming to achieve high-performance DSSCs. Five different solvents—ethanol, isopropanol, distilled water, methanol, and Zamzam water—are explored to optimize the extraction process of the natural dyes. The doctor blade technique is employed to coat TiO2 nanomaterials onto ITO glass substrates. UV–Vis spectrophotometry and FTIR spectroscopy are used to characterize the optical properties and structural composition of the dyes, revealing that flavonoid/tannin groups are the primary compounds responsible for light harvesting. The DSSC performance is evaluated under a 30 W lamp, adjusted to light intensity of 10 mW/cm2. As a result, the DSSCs using gambier leaf extract as photosensitizer demonstrate the highest recorded efficiency of 4.71 %, with a Jsc of 2.95 mAcm−2 and a Voc of 0.64 V. These findings contribute to advancing DSSC technology by leveraging the potential of natural photosensitizers for sustainable energy conversion applications.