A new calcining-leaching process was used to extract high purity alumina (Al2O3) powders from fly ash in this study. The fly ash was mixed with soda (Na2CO3) and calcined at 900 ℃ to yield soluble aluminates. Subsequently the calcined ash was leached with sulfuric acid (H2SO4) to produce a solution containing aluminum. The unwanted metal ions including Fe3+ and Na+ were removed by ethylene diamine tetraacetic acid (EDTA) and water washing. Then added the proper dispersant, controlling the crystallization of aluminum trihydroxide precipitation, and the drying and calcining process was carried out, resulting in ultra fine Al2O3 powders with high purity. The characteristics of the Al2O3 powders were examined by means of X-ray diffraction, transmission electron microscope and the Brunauer, Emmet and Teller (BET) surface analysis method. The extraction efficiency of Al2O3 can surpass 98%by optimization of the calcination and lixiviation processes. Well-dispersed fibriform γ-Al2O3 powders were obtained by calcining at 800 ℃ and the purity of the ultra fine Al2O3 powders was more than 99.6%.