This study used Type I Portland cement with Na2Oeq of 0.67% to fabricate a mortar specimen with w/c ratio of 0.5 and a dimension of φ10 3 cm. The 7 volume fractions of aggregate (Vf) were adjusted to 0, 10, 20, 30, 40, 50 and 60%, and Acceleration Lithium Migration Technique (ALMT) experiments with 9 A/m2 constant current density were performed. The results show that for specimen with Vf of 10%, the negative effects on ion migration generated by aggregate dilution and tortuosity effects were the greatest; therefore, the removal times of Na + and K+, the time it took for Li+ to pass through the specimen and the time for Li+ to reach steady state were all longer than in the other experiments. When Vf was increased to 20 and 30%, the negative effect from the dilution and the tortuosity effects generated by the increase in Vf was cancelled the positive effect from ITZ on ion migration. When Vf was increased to over 30%, the percolation effect from ITZ controlled the behavior of ion migration. During the ALMT experiment, the anode steadily produced a large amount of O2, while the cathode produced a small amount of H2.