The present study describes the hydrochemistry of ground waters found in the Mesta River Basin, located in the south-western part of Bulgaria. The groundwater’s composition can be expressed as follows: Ca2+ > Na+ > Mg2+ > K+; Ca2+ > Mg2+ > Na+ > K+ in equivalent units for the cations, and HCO3– > SO42– > Cl– in equivalent units for the anions. The chemical composition of the studied groundwater can be described as calcium-bicarbonate. The calcium ions make up from 17.90% to 38.62% (30.18% on average), and the bicarbonate ions make up from 35.30% to 48.98% (43.70% on average) of all ions. Taken together, the calcium and bicarbonate ions make up from 61.44% to 87.60% (73.88% on average) of all ions. The groundwater itself is of slightly alkaline nature, having pH of 7.3 to 8.6, and TDS of 67 mg/l to 611 mg/l. One groundwater sample from the Mesta River catchment area was found to be of the low-mineralized type (TDS = 193 mg/l) alkaline water (pH = 9.8) in the Mesta Lowlands – the Banichan groundwater mineral source. The water can be described as sodium-bicarbonate, with sodium ions making up to 93.5% of the cations, and bicarbonate ions – 69.6% of the anions. Out of all ions, the sodium ions were found to be 48%, and the bicarbonate ions – 33.86%. The sequence of ions is in the following order: Na+ > Ca2+ > Mg2+ > K+, and HCO3– > Cl– > SO42– > CO32–.