Boiler slagging jeopardizes the safe and economic operation of coal-fired boilers. Aluminosilicates are the most abundant substances in fly ash and boiler slagging deposits. In order to understand the roles of the fly ash aluminosilicates in slagging, studying their evolution in the ash deposition is invaluable. In this work, 27 Al magic angle spinning nuclear magnetic resonance (MAS-NMR) and X-ray diffraction were used to measure the aluminum coordination and the phase distribution in fly ash and ash deposit samples of two USA thermal coals [Powder River Basin (PRB) sub-bituminous coal and Illinois coal] and their blended coal prepared in an oxy-coal combustion experiment apparatus. Morphology and constituents of these samples were also analyzed using scanning electronic microscopy. The results show that, for all fly ashes and ash deposits, the aluminum exists only in aluminosilicates and is mainly four-coordinate aluminum [Al(IV)], with a small amount in sixcoordinate aluminum Al(VI) (chemical shift: 2.8 ppm). The formation of spinning sidebands due to the paramagnetic effect of the Fe-bearing species in fly ash increases difficulty in resolving the NMR spectra of fly ash aluminosilicates. The aluminosilicates in the PRB coal fly ash are mainly amorphous and also contain low-crystallinity gehlenite; the aluminosilicates in the Illinois coal fly ash are basically amorphous, and the Fe-containing materials in the fly ash generate stronger spinning sidebands of Al(IV) in its 27 Al MAS-NMR spectra. During ash deposition, the evolutions of fly ash aluminosilicates for the coals are different. For PRB coal, fly ash aluminosilicates hardly react with foreign active metal elements after being deposited on a deposition probe in the furnace, even though the fly ash contains a large amount of calcium. For the Illinois coal, the easily melting aluminosilicates in ash deposition increase. The ash deposition for the blended coal demonstrates that the easily melting aluminosilicates in fly ash continue to combine with foreign iron and calcium ions in the ash deposition process, which can deteriorate the ash deposition. Therefore, the easily melting aluminosilicates should receive more attention for the understanding and control of slagging.