AA5182 (Al-4.5 wt% Mg) can become susceptible to intergranular corrosion (IGC) with time at moderately elevated service temperatures owing to precipitation of Mg-rich β-phase at grain boundaries, which can lead to stress corrosion cracking (SCC). The IGC and SCC susceptibility of AA5182 was found to depend strongly on sensitisation heat treatments. AFM and TEM studies demonstrated that the degree of precipitation and thus susceptibility to attack for a boundary can be related to its crystallographic misorientation. Low angle boundaries (<20°) are most resistant to attack as they do not show β-phase precipitation. However, higher angle boundaries show highly variable precipitation and corrosion susceptibility: critical factors are the grain boundary plane and precipitate/matrix crystallographic relationship.