An occurrence of tetra-coordinated aluminum in altered coal and low temperature coal ashes was investigated. As altered coal a sample from the Lazy mine (Upper Silesian Coal Basin) was tested, further, low-temperature ashes from different coals were prepared and measured. During preparation the selected coal samples were intensively air-oxidized; 27Al MAS NMR spectra of obtained ashes were then acquired and compared against those for initial coals. A reference wood ash and Al standards were used for identification of Al-forms. It was found that chemical shift at 4 ppm with coals corresponds to that for triaquo-hydroxo-diphenoxido-aluminum(III) complex (THDA), further, the shift at 72 ppm with altered coal and resulting ashes agrees with that for Al tetra-coordinated with oxygen. So, in the presence of coal organics the tetra-coordinated Al is formed under low temperature conditions, because during low temperature ashing the THDA complex is transformed to Al tetra-coordinated with oxygen only at 350 °C. A similar process occurred in the case of oxidation of coal substance under low temperature conditions in the nature at temperatures below 150 °C., Pavel Straka., and Obsahuje bibliografii