Daily temperature variations induce phase transitions and lattice strains in halide perovskites, challenging their stability in solar cells. We stabilized the perovskite black phase and improved solar cell performance using the ordered dipolar structure of β-poly(1,1-difluoroethylene) to control perovskite film crystallization and energy alignment. We demonstrated p-i-n perovskite solar cells with a record power conversion efficiency of 24.6% over 18 square millimeters and 23.1% over 1 square centimeter, which retained 96 and 88% of the efficiency after 1000 hours of 1-sun maximum power point tracking at 25° and 75°C, respectively. Devices under rapid thermal cycling between −60° and +80°C showed no sign of fatigue, demonstrating the impact of the ordered dipolar structure on the operational stability of perovskite solar cells.