The effects of critical defects on stress corrosion cracking (SCC) of Al–7.82Zn–1.99Mg–2.41Cu–0.12Zr alloy under under-ageing (UA), peak-ageing (PA) double-ageing (DA) and retrogression and reageing (RRA) were investigated. It is found that anodic dissolution of grain boundary precipitates (GBPs) for UA sample generates critical defects due to low Cu content of GBPs, whereas the dissolution of Al, Mg and Zn elements within the grain interior is responsible for the formation of critical defects for PA, DA and RRA samples. The high distribution continuity of GBPs promotes the continuous propagation of stress corrosion crack along grain boundary, leading to intergranular SCC for UA sample. Coarsened GBPs which are distributed discontinuously could hinder anodic dissolution along the grain boundary. As a result, the cracks propagate along the grain interior, causing transgranular SCC for DA sample. And large size and low density of matrix precipitates (MPTs) decease SCC susceptibility. Al7Cu2Fe particles promote the dissolution of the surrounding matrix, inducing local stress concentration, and thus leading to the generation of stress corrosion cracks.