A comprehensive numerical analysis of the thermal performance of monocrystalline silicon solar cells was conducted to examine the influence of back-contact material type and thickness. Simulations were performed using the COMSOL Multiphysics package, focusing on three representative materials; aluminum, copper, and silver—selected for their distinct thermal conductivities and relevance in photovoltaic applications. The results show that increasing back-contact thickness from 15 μm to 45 μm produced only a marginal reduction in operating temperature, with a maximum variation of 0.76 °C. Conversely, the choice of material exerted a significant effect on thermal behavior. Silver exhibited the most favorable performance, achieving a maximum cell temperature of 63.70 °C, while copper offered a slightly higher value of 66.60 °C but with improved cost-effectiveness. Aluminum, despite being the most economical option, resulted in the poorest thermal management, with maximum cell temperatures reaching 75.90 °C. These findings highlight the importance of back-contact material selection in enhancing thermal stability, efficiency, and lifespan of photovoltaic devices, and provide valuable guidance for the design of sustainable, high-performance solar cells.