The aim of this study is to characterize in detail, the mineralogy of different-shaped concretions as well as to investigate the physico-chemical parameters of the associated mine drainage and drip waters in the Santa Barbara level of the Libiola Mine (NW Italy) by several geochemical and mineralogical techniques. Under the term “minothems” we are grouping all those secondary minerals that occur under certain form or shape related to the conditions under which they formed but occur in a mine, or in any artificial underground environment (i.e., "mine speleothems"). Different types of minothems (soda straw stalactites, stalactites, and draperies) were sampled and analyzed. Mineralogical results showed that all the samples of stalactites, stalagmite and draperies are characterized by poorly crystalline goethite. There are significant differences either in their texture and chemistry. Stalactites are enriched in Zn, Cd, and Co in respect to other minothems and show botryoidal textures; some of these exhibit a concentric layering marked by the alternation of botryoidal and fibrous-radiating textures; the draperies are enriched in V and show aggregates of sub-spheroidal goethite forming compact mosaic textures. Geochemical investigations show that the composition and physico-chemical parameters of mine drainage and drip waters are different from the other acidic mine water occurrences in different areas of the Libiola Mine, where minothems are less abundant. All mine water samples contain Cu, Ni, and Zn in appreciable levels, and the physico-chemical conditions are consistent with the stability of ferrihydrite, which however tends to transform into goethite upon ageing.