A high alkali reactive aggregate-zeolitization perlite was used to test the long-term effectiveness of LiOH in inhibiting alkali-silica reaction. In this paper, the rigorous conditions were designed that the mortar bars had been cured at 80°C for 3 years after autoclaved 24 hours at 150°C. Under this condition, LiOH was able to inhibit the alkali-silica reaction long-term effectiveness. Not only the relationship between the molar ratio of n (Li)/(Na) and the alkali contents in systems was established, but also the governing mechanism of such effects was also studied by SEM.