This study investigated the mineralogical and chemical characteristics of ochreous precipitates and mine water samples from abandoned Upper Carboniferous hard coal mines in an extensive former mining area in western Germany. Mine water characteristics have been monitored and assessed using a multi-methodological approach. Thirteen mine water discharge locations were sampled for hydrochemical analysis, with a total of 46 water samples seasonally collected in the whole study area for stable isotopic analyses. Mineralogical composition of 13 ochreous precipitates was identified by a combination of powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM/EDS). Results showed that abandoned mine drainage was characterized by circumneutral pH, Eh values ranging from 163 to 269 mV, relatively low concentrations of Fe and Mn, and was dominated by HCO3− > SO42− > Cl− > NO3− and Na+ > Ca2+ > Mg2+ > K+. Goethite and ferrihydrite were the dominant precipitated Fe minerals, with traces of quartz, dolomite, and clay minerals. Some metal and metalloid elements (Mn, Al, Si, and Ti) were found in the ochreous sediments. The role of bacteria in the formation of secondary minerals was assessed with the detection of Leptothrix ochracea. The δ18O and δ2H values of mine water plotted on and close to the GMWL and LMWLs indicated local derivation from meteoric water and represented the annual mean precipitation isotopic composition. Results might help to develop strategies for the management of water resources, contaminated mine water, and public health.