The geochemical and isotopic composition of groundwater in the Velenje Basin, Slovenia, was investigated between the years 2014 to 2015 to identify the geochemical processes in the major aquifers (Pliocene and Triassic) and the water-rock interactions. Thirty-eight samples of groundwater were taken from the aquifers, 19 in the mine and 19 from the surface. Groundwater in the Triassic aquifer is dominated by HCO , and Si, and has high alkalinity, with δ
13C DIC values in the range of -14.4 to +4.6 ‰. Based on the δ
13C DIC values in all the aquifers (Pliocene and Triassic), both processes influence the dissolution of carbonate minerals and dissolution of organic matter and in the Pliocene aquifers, methanogenesis as well. Based on Principal Component Analysis (PCA), and on geochemical and isotopic data we conclude that the following types of groundwater in Velenje Basin are present: Triassic aquifers with higher pH and lower conductivity and chloride, Pliocene, Pliocene 1 and Pliocene 2 aquifers with lower pH and higher conductivity and chloride contents, and Pliocene 3 and Pliocene 2, 3 aquifers with the highest pH values and lowest conductivities and chloride contents.