Abstract: To advance the technical development of harmless disposal and resource recovery for retired photovoltaic modules, this study investigates the pyrolysis behaviors of photovoltaic backsheets, which are typical waste materials from photovoltaic laminates. The effects of pyrolysis temperature, holding time and oxidative atmosphere on the distribution and composition of pyrolysis products were systematically explored. Experimental results indicate that the thermal decomposition of photovoltaic backsheets primarily occurs within the temperature range of 400–600 ℃, and pyrolysis temperature dominates product yield and energy consumption performance. By comprehensively considering liquid product yield and overall energy consumption, 450 ℃ was determined as the optimal pyrolysis temperature for backsheet treatment. Liquid pyrolysis products are mainly composed of carboxylic substances with a small amount of fluorine-containing organic compounds, while gaseous products principally consist of carbon monoxide and carbon dioxide. Extended pyrolysis duration induces secondary cracking of liquid components and promotes the conversion of liquid products into small-molecule gaseous products, thereby improving gas product yield. Oxidative atmosphere exerts distinct temperature-dependent effects on the pyrolysis process. Low-temperature oxidation reduces the activation energy of backsheet decomposition and facilitates the stable generation of liquid and solid products, whereas high-temperature oxidation intensifies the deep cracking of liquid products and accelerates the oxidation of pyrolytic char. Microscopic morphology analysis reveals that the pyrolysis procedure includes sequential stages of melting, thermal decomposition, volatile release and carbonization. Sufficient pyrolysis produces porous and fluffy char with promising potential for resource reuse. both liquid and solid products. However, high temperatures intensified the decomposition of liquid products and the oxidation of pyrolytic char. Based on the morphology of the pyrolytic char, it can be inferred that the backsheet pyrolysis undergoes stages of melting, pyrolysis, release of volatiles, and carbonization. And abundant loose and porous structures were obtained in pyrolytic char.