On the basis of solid-state NMR measurements organoaluminium complexes in coal substance are presented. Solid extracts obtained from the Ostrava-Karviná bituminous coal and from the North Bohemian brown coal were used. It was found that the significant chemical shift at 13.5–14.8 ppm corresponds to that obtained for the hexaphenolatoaluminium complex (14.2 ppm). This shift can be also ascribed to the Al-naphthalocyanine complex. Hence, organoaluminium compounds coordinated to six oxygens are present in coal substance.