Five unique mineral assemblages that include the sulfates millosevichite, alunogen, anhydrite, tschermigite, coquimbite, voltaite, and godovikovite, as well as the halide salammoniac and an unidentified phase, according to X-ray diffraction and EDS data, were found as encrustations on quartzofeldspathic sand and sandstone adjacent to coal-fire gas vents associated with underground coal fires in the Wuda coalfield of Inner Mongolia. The mineral assemblage of alunogen, coquimbite, voltaite, and the unidentified phase collected front the same gas vent, is documented for the first time. Observations suggest that the sulfates millosevichite, alunogen, coquimbite, voltaite, godovikovite, and the unidentified phase, crystallized in response to a complex sequence of processes that include condensation, hydrothermal alteration, crystallization from solution, fluctuating vent temperatures, boiling, and dehydration reactions, whereas the halide salammoniac crystallized during the sublimation of coal-fire gas. Tschermigite and anhydrite formed by the reaction of coal-fire gas with quartzofelds pathic rock or by hydrothermal alteration of this rock and crystallization from an acid-rich aqueous solution. These minerals have potentially important environmental significance and may be vectors for the transmission of toxins. Coal fires also provide insight for the recognition in the geologic record of preserved mineral assemblages that are diagnostic of ancient fires.