The study presents composition data of 87 surface water samples from high alpine catchments of the Zermatt area (Swiss Alps). The investigated area covers 170 km2. It was found that the surface runoff acquires the dissolved solids mostly by reaction of precipitation water with the minerals of the bedrock. Total dissolved solids (TDS) vary from 6 to 268 mg L−1. All collected water shows a clear chemical signature of the bedrock mineralogy. The contribution of atmospheric input is restricted to small amounts of ammonium nitrate and sodium chloride. NH4 is a transient component and has not been detected in the runoff. Evaporation is not a significant mechanism for TDS increase in the Zermatt area. The chemical composition of the three main types of water can be related to the mineralogy of the dominant bedrock in the catchments. Specifically, Ca-HCO3 (CC) waters develop from metamorphic mafic rocks and from carbonate-bearing schists. Mg-HCO3 water originates from serpentinites and peridotites. Ca-SO4 (CS) waters derive from continental basement rocks such as pyrite-rich granite and gneiss containing oligoclase or andesine. The collected data suggest that, together with reaction time, modal sulfide primarily controls and limits TDS of the waters by providing sulfuric acid for calcite (CC waters) and silicate (CS waters) dissolution. If calcite is present in the bedrock, its dissolution neutralizes the acid produced by sulphide weathering and buffers pH to near neutral to weakly alkaline conditions. If calcite is absent, the process produces low-pH waters in gneiss and granite catchments. The type of bedrock and its mineral assemblage can be recognized in water leaving very small catchments of some km2 area. The large variety of water with a characteristic chemical signature is an impressive consequence of the richly diverse geology and the different rock inventory of the local catchments in the Zermatt area.