High aluminum coal (HAC, Al2O3 in its ash content ranges 38-51%) is abundant and plays an important role in energy and chemical product in China. The ash fusion characteristics of HAC and its modification behaviors by coal blending or flux were investigated by ash fusion temperature (AFT) analyzer, X-ray fluorescence spectrometry, X-ray diffractometry combined with normalized reference intensity ratio method, and scanning electron microscopy. The AFT variation is manly dependent on mineral composition and its transformation. A large amount of high melting point (MP) mullite formation results in HAC (Sunjiahao coal, SJH) AFT high. Compare with the coal blending of Shenmu (SM) and Xiangyuan (XY), CaO addition provides a better way to adjust ash fusion characteristics of SJH. For coal blending, that calcium and iron element in low AFT coal react with high MP mineral and then evolve into eutectic and amorphous matter makes the AFT of SJH mixtures decrease. The formations of low MP anorthite, and gehlenite, and their eutectic resulting from the reaction of CaO and mullite lead to a decrease in the AFT.