To utilize CFBC Al-rich fly ash, a mild hydrochemical extraction process was investigated for recovery of alumina. An alumina extraction efficiency of 92.31%was attained using a 45%NaOH solution, an original caustic ratio (molar ratio of Na2O to Al2O3 in the sodium aluminate solution) of 25, a molar ratio of CaO to SiO2 in the fly ash of 1.1, a liquid volume to solid mass ratio of 9, a reaction temperature of 280 ℃, and a residence time of 1 h when treating fly ash with an alumina to silica mass ratio (A/S) of 0.78 and an alumina content of 32.43%. Additionally, the alumina leaching mechanism was explored via structural and chemical analysis, which revealed that after alkaline digestion, the main solid phase containing silica was NaCaHSiO4 with a theoretical A/S of zero.