The penetration of Ga along Al grain boundaries under stress-free conditions is investigated in the present study. In-situ SEM observations indicate that the penetration rate of Ga along Al grain boundaries at room temperature ranged from 6.4 to 9.2 μm/s, which is similar to the rate of diffusion in the liquid state. For a specific high energy grain boundary, the grain boundary misorientation is determined from the TEM diffraction Kikuchi pattern, and a molecular statics simulation method was employed to investigate grain boundary structure. A comparison of the structure of this high energy boundary is made with the Σ11(131) tilt grain boundary that is not penetrated by Ga in the absence of the applied stress. The results indicate that the grain boundary plane void structure in the high energy grain boundary may provide void channels for Ga monolayer penetration. In addition, penetration behavior investigated under different length scales supports this model.