The anisotropic corrosion behavior of aluminum was investigated under the applied residual stress state with elastic and plastic deformations. Under the initiation stage in the electrochemical response of aluminum with the residual stress, grain orientations play a crucial role in nucleating pits, with an impact on work function. However, in the propagation stage, a clear correlation between the residual stress, work function, and the corrosion rate is demonstrated. The differences in the corrosion rate of grains are attributed to the residual stress concentration and sensitivity, which are resulting from the mechanical properties of each grain. With the residual stress concentration and grain properties, grains close to (111) with higher work function corroded faster, in contrast, grains close to (100) with low work function have a slower corrosion rate. Work function calculated based on coordination numbers and first-principle calculations performed, and correspond to each other, with support the experimental results observed.