All-inorganic perovskites are promising candidates for solar energy and optoelectronic applications, despite their polycrystalline nature with a large density of grain boundaries (GBs) due to facile solution-processed fabrication. GBs exhibit complex atomistic structures undergoing slow rearrangements. By studying evolution of the Σ5(210) CsPbBr3 GB on a nanosecond time scale, comparable to charge carrier lifetimes, we demonstrate that GB deformations appear every ∼100 ps and increase significantly the probability of deep charge traps. However, the deep traps form only transiently for a few hundred femtoseconds. In contrast, shallow traps appear continuously at the GB. Shallow traps are localized in the GB layer, while deep traps are in a sublayer, which is still distorted from the pristine structure and can be jammed in unfavorable conformations. The GB electronic properties correlate with bond angles, with notable exception of the Br-Br distance, which provides a signature of halide migration along GBs. The transient nature of trap states and localization of electrons and holes at different parts of GBs indicate that charge carrier lifetimes should be long. At the same time, charge mobility can be reduced. The complex, multiscale evolution of geometric and electronic structures of GBs rationalize the contradictory statements made in the literature regarding both benign and detrimental roles of GBs in perovskite performance and provide new atomistic insights into perovskite properties.