The sulfating reaction of coal fly ash with ammonium sulfate and the microwave extraction of aluminum ions from the resultant materials using sulfuric acid have been investigated. The (NH$_4$)$_3$Al(SO$_4$)$_3$ formed by the reaction of coal fly ash and ammonium sulfate decomposed to NH$_4$Al(SO$_4$)$_2$ at $geq$ 350$^{circ}C$. The maximum efficiency of aluminum ions extracted from the sulfating reaction product (400$^{circ}C$, 120 min) by microwave heating (90$^{circ}C$, 240 min) using 1 M H$_2$SO$_4$ was 84％ (based on Al content in coal fly ash) but 77％ by conventional heating at same condition.