AbstractThe global climate change negatively affects the photovoltaic performance of traditional solar cell technologies. This article investigates the potential of organic photovoltaics (OPV) for high‐temperature environments, ranging from urban hot summers (30—40 °C) and desert regions (65 °C) up to (aero) space conditions (130 °C), the thermal window in which OPV can operate. The approach is based on a combination of experiments and simulations up to 180 °C, moving significantly beyond the conventional temperature ranges reported in the literature. New 2H‐benzo[d][1,2,3]triazole‐5,6‐dicarboxylic imide‐based copolymers with decomposition onset temperatures above 340 °C are used for this study, in combination with non‐fullerene acceptors. Contrary to their inorganic counterparts, OPV devices show a positive temperature coefficient up to ≈90 °C. At temperatures of 150 °C, they are still operational, retaining their room temperature efficiency. Complementary simulations are performed using an in‐house developed software package that numerically solves the drift‐diffusion equations to understand the general trends in the obtained current–voltage characteristics and the materials’ intrinsic behavior as a function of temperature. The presented methodology of combined high‐temperature experiments and simulations can be further applied to investigate the thermal window of operation for other OPV material systems, opening novel high‐temperature application routes.