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The intergranular corrosion and β phase evolution of 5083 aluminum alloy containing Er and Zr during annealing at 100–230 °C were studied using mass loss tests and transmission electron microscopy. The mass loss curves showed that when annealing temperature changed from 200 to 220 °C, the alloy was subjected to a transition from sensitized state to stabilized state, corresponding to the change of nucleation position of β precipitates from grain boundaries to triple junctions. Particularly, when the annealing temperature was at 210 °C, this transition could also happen when the annealing time was increased from 0.5-10 h to 15-24 h, associated with the change in the shape of β precipitates. The classical nucleation analysis with the consideration of Mg segregation showed the nucleation rates at grain boundary and triple junction were 1013 and 1011 m−3 s−1 at sensitization temperature 150 °C, but 109 and 1010 m−3 s−1 at stabilization temperature 220 °C, suggesting the change of nucleation site with increasing temperature. The analysis of diffusion flux of Mg around β precipitate suggested that the shape change of β precipitates from elongate to spheroidal at 210 °C was attributed to the dominant interface diffusion over the grain boundary diffusion with the increase of time. Keywords: Aluminum alloy, Microstructure, Corrosion, Classical nucleation theory, Diffusion