Abstract: The extraction of alumina from coal fly ash as one of the important value-added ways causes wide concerns. The extraction of alumina and lithium simultaneously is of great significance to the improvement of the utilization efficiency since the coal fly ash contains a certain amount of lithium. To clear understand the dissolution characteristics of lithium (Li) in fly ash, the dissolution characteristics of Li in acidic solution and alkaline solution from the original fly ash, activated by CaO and Na₂CO₃ were investigated respectively, and the phase transformations of fly ash before and after leaching were analyzed by X-Ray diffraction. The results show that the fly ash directly leached by acidic solution and alkaline solution presented a relatively lower dissolution of Li (28% and 36%, respectively) at 100℃. The dissolutions of lithium, however, were significantly improved after coal fly ash activated by CaO and Na₂CO₃. The dissolutions of Li in acidic solution reached 98% and 86% after the fly ash activated by CaO and Na₂CO₃, which were higher than those in alkaline solution (86% and 67%). The XRD analysis results demonstrate that some Li is easier to be leached by acid or alkali which might be deposited in the amorphous or the surfaces of crystalline minerals. Some Li might be embedded in mullite, quartz and other crystalline phase and leached hardly. However, they were again embedded in calcium melilite and nepheline after CaO and Na₂CO₃ activation and the dissolution of Li were increased. The dissolution of Li in acidic solution was generally higher than that in alkaline solution owing to the reaction between calcium melilite and nepheline with acid is easier than those with alkali.