Connection of microstructure with corrosion properties of an Al-3.62Cu-0.9Mg-0.45Ag alloy in natural aging (NA) state and peak aging (PA) state at different final rolling temperatures (20 °C, 180 °C and 280 °C) are studied by scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), X-ray diffraction (XRD), texture and electrochemical analysis. The results show that the deformation texture and recrystallization texture of T280-NA alloy account for the largest percentage with the largest degree of recrystallization. With the increase of final rolling temperature, the proportion of low angle grain boundaries (LAGBs) of NA alloy increases, the diameter, thickness and volume fraction of Ω phase in PA alloy decrease, and the grain boundary precipitates (GBPs) are gradually transformed from discontinuous distribution to continuous distribution. The grain boundary precipitates are also found to be consist of alternating S and θ phases and the width of precipitation free zones (PFZs) is essentially independent of final rolling temperature. The intergranular corrosion (IGC) resistance of T280-NA alloy and T20-PA alloy is the best, which is a result of the combined effect of GBPs, texture and grain boundary properties. In addition, this result is verified in this paper by studying the electrochemical properties of the alloy.