This study presents an experimental and thermodynamic investigation of a solar photovoltaic (PV) system integrated with a thermoelectric cooler (TEC)-based cooling arrangement. Three configurations were analyzed under identical outdoor conditions. (i) a conventional PV module without cooling, (ii) integrated with a bismuth telluride (Bi₂Te₃) module, (iii) with a lead telluride (PbTe) thermoelectric system. The performance comparison was carried out in terms of temperature reduction, electrical output, exergy input, hybrid system exergy efficiency (HSEE), and hybrid system exergy destruction (HSED). Experimental results indicate that the integration of thermoelectric materials significantly reduces the operating temperature of the PV module. The module with Bi₂Te₃ exhibited the lowest peak surface temperature (51.4 ± 1.0 °C) compared to the conventional system (55.6 ±1.0 °C) and the PbTe-based system (53.2 ±1.0 °C) lies in between. Correspondingly, the net electrical output improved from 8.93 ± 0.27 W (without TEC) to 10.59 ± 0.32 W with Bi₂Te₃ and to 9.63 ± 0.29 W with PbTe, demonstrating enhanced energy conversion performance. Exergy analysis revealed that the hybrid PV-TEC systems possess improved HSEE due to reduced thermal losses and lower entropy generation. The decrease in operating temperature minimizes irreversibilities associated with heat dissipation, thereby reducing HSED. Among the tested materials, Bi₂Te₃ showed better HSEE (15.37% more compared to no TEC), leading to cooling effectiveness. The study confirms that thermoelectric cooling effectively reduces PV operating temperature and enhances PV-side electrical behaviour. However net thermodynamic benefit depends on the trade-off between improved PV output and TEC power consumption. This hybrid approach offers a promising pathway for enhancing the overall performance and sustainability of solar energy systems.