AbstractFully inorganic perovskite nanocrystals (NCs) have been widely investigated due to their potential as very interesting active materials for several types of photonic and optoelectronic devices. Despite several experiments designed to investigate the basic emission properties of these NCs, a clear and complete understanding of their photophysics is still missing. In this work, temperature‐dependent steady state and time‐resolved photoluminescence (PL) measurements are used to investigate the nature of the emitting states, the origin of the excitation relaxation dynamics and the effects of aging upon long exposure to wet air for thin films of CsPbBr₃ NCs prepared by coprecipitation. It is demonstrated that both free excitons and localized excitons contribute to the NC emission and that electron traps within the conduction band, ≈14 meV and ≈80 meV above the band edge, determine thermal emission quenching. Moreover, it is shown that the non‐exponential PL relaxation dynamics are due to short‐range energy migration within a disordered distribution of localized states between 10 and 100 K, with activation of a second, long‐range diffusion process at higher temperatures. It is also demonstrated that aging determines the variations in defect levels, exciton‐phonon coupling and exciton relaxation dynamics. The results substantially improve the current understanding of the basic photophysics of CsPbBr₃ NC films and of the aging effects and are expected to provide a useful guide for future characterization of other similar materials.