The mine drainage of the Ibbenbüren anthracite coal mine is characterized by exceptionally high concentrations of dissolved iron and sulfate. The elevated position of the coal field with respect to the surrounding area makes the neighboring sediments an unlikely source of these elements. Accordingly, it has been hypothesized that interaction between infiltrating rainwater and the fractured overburden is a key process governing the mine drainage chemistry. To test this hypothesis, two full-diameter core samples drilled above the discharging adit of the coal mine were investigated. The methodology combined several analytical techniques to identify and characterize traces of water–rock interaction related to both diagenesis and relatively recent weathering processes along open fractures. The coupled appearance of kaolinite-dickite-illite minerals in weathered and unweathered rock sections was clearly connected to the burial history of the Carboniferous sequence. In contrast, the formation of iron (oxide-) hydroxides together with the presence of oxidized pyrite in weathering profiles along both sides of the fractures was positively related to the geochemical footprint of the coal mine drainage. Thus, open fractures, possibly originated from mining activities, may play a significant role in the drainage chemistry, especially considering the rather poor hydraulic conditions of the overburden.