Formamidinium lead triiodide (FAPbI₃ ) is attractive for photovoltaic devices due to its optimal bandgap at around 1.45 eV and improved thermal stability compared with methylammonium-based perovskites. Crystallization of phase-pure α-FAPbI₃ conventionally requires high-temperature thermal annealing at 150 °C whilst the obtained α-FAPbI₃ is metastable at room temperature. Here, aerosol-assisted crystallization (AAC) is reported, which converts yellow δ-FAPbI₃ into black α-FAPbI₃ at only 100 °C using precursor solutions containing only lead iodide and formamidinium iodide with no chemical additives. The obtained α-FAPbI₃ exhibits remarkably enhanced stability compared to the 150 °C annealed counterparts, in combination with improvements in film crystallinity and photoluminescence yield. Using X-ray diffraction, X-ray scattering, and density functional theory simulation, it is identified that relaxation of residual tensile strains, achieved through the lower annealing temperature and post-crystallization crystal growth during AAC, is the key factor that facilitates the formation of phase-stable α-FAPbI₃ . This overcomes the strain-induced lattice expansion that is known to cause the metastability of α-FAPbI₃ . Accordingly, pure FAPbI₃ p-i-n solar cells are reported, facilitated by the low-temperature (≤100 °C) AAC processing, which demonstrates increases of both power conversion efficiency and operational stability compared to devices fabricated using 150 °C annealed films.