In this study, the performance of a Photovoltaic Thermal-Organic Rankine Cycle (PVT-ORC) system combined with a Proton Exchange Membrane Electrolysis Cell (PEMEC) is investigated. A combined numerical/theoretical model of the system is developed and used to evaluate the effect of various system design parameters. In addition, the effects of using water, ethylene glycol, and a mixture of water and ethylene glycol (50/50) as the working fluid of the PVT system and R134a, R410a, and R407c as the working fluid of the ORC cycle on the performance of the PVT-ORC-PEMEC system are studied. Based on the results, R134a and water demonstrated the best performance as the working fluid of the ORC and PVT systems. Moreover, the electrical efficiency of the combined PVT-ORC system is 15.65% higher than the electrical efficiency of the conventional PVT system. Also, the maximum hydrogen production rate of the proposed PVT-ORC-PEMEC system is calculated to be 1.70 mol/h.