With a sharp increase in photovoltaic (PV) installations across the world, PV waste is now a relatively new addition to the e-waste category. From 45,000 tonnes in 2016, the PV waste stream is rapidly increasing and is projected to reach 60 million tonnes by 2050. Backsheets are composite structures made from several material layers of polymer, adhesive, and primer. Widely used PV backsheets can be classified into three core types: (a) KPK (Kynar/polyethylene terephthalate (PET)/Kynar), (b) TPT (Tedlar/PET/Tedlar), and (c) PPE (PET/PET/ethylvinylacetate). Kynar and Tedlar are based on polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF), respectively. PPE backsheets are fluorine-free composites made primarily from PET. With increasing focus on the end-of-life (EoL) handling of PV waste, the handling of fluoropolymers, which is largely unexplored, requires closer examination to avoid environmental damage. The aim of this study was to obtain information on the fluorine released from PV backsheet materials into the gas phase during combustion and pyrolysis as EoL pathways. Therefore, several experimental trials were conducted to measure fluorine transfer into the gas phase at 300 °C, 400 °C, 500 °C, and 900 °C (for pyrolysis) and at 750 °C, 850 °C, and 950 °C (for incineration).