Most solar energy incident (>70%) upon commercial photovoltaic panels is dissipated as heat, increasing their operating temperature, and leading to significant deterioration in electrical performance. The solar utilisation efficiency of commercial photovoltaic panels is typically below 25%. Here, we demonstrate a hybrid multi-generation photovoltaic leaf concept that employs a biomimetic transpiration structure made of eco-friendly, low-cost and widely-available materials for effective passive thermal management and multi-generation. We demonstrate experimentally that bio-inspired transpiration can remove ~590 W/m2of heat from a photovoltaic cell, reducing the cell temperature by ~26 °C under an irradiance of 1000 W/m2, and resulting in a relatively 13.6% increase in electrical efficiency. Furthermore, the photovoltaic leaf is capable of synergistically utilising the recovered heat to co-generate additional thermal energy and freshwater simultaneously within the same component, significantly elevating the overall solar utilisation efficiency from 13.2% to over 74.5%, along with over 1.1 L/h/m2of clean water.