Bifacial solar modules, capable of harvesting sunlight from both sides, present a promising pathway for sustainable energy generation. This study examines the performance of bifacial modules on a cloudy day through comparative exergy and energy analyses. The analysis considers both the quality and quantity of energy produced by bifacial and monofacial modules. Conducted at Qassim University in Buraydah City, Saudi Arabia, the study recorded measurements during two intervals on a cloudy day using a real-time photovoltaic measurement system. Module performance was evaluated concerning energy yield, exergy yield, and solar irradiance, factoring in ambient and module temperatures. The results demonstrate that bifacial modules outperformed monofacial modules in electrical energy and output exergy. In the first period, the bifacial modules showed a 9.5% higher exergy efficiency and a 7% greater energy efficiency compared to the monofacial modules. During the second period, the bifacial modules achieved a 4.5% higher exergy efficiency and a 3.5% increased energy efficiency over the monofacial modules. These findings contribute to global sustainability efforts by reducing fossil fuel dependence and optimizing bifacial PV module design and operation for enhanced energy and exergy efficiency, even in cloudy conditions. The study’s implications for sustainable development and energy policies underscore the essential role of advanced PV technologies in achieving sustainable energy goals.