The Llobregat and Ter Rivers, typical Mediterranean catchments in Northeast Spain, supply water to more than 4.5 million inhabitants residing in the metropolitan area of Barcelona. The objective of this work is to study the factors that influence the surface water quality of Llobregat catchment. As such, spatial and temporal variations of more 50 water chemical parameters were monitored in 10 sampling sites for a period that extended from July 1996 to December 2000. The temperature, pH and conductivity were measured at sites, whereas metals were analysed using ICP-OES and ICP-MS instrumental techniques. The head waters of the Llobregat River catchment flow through detrital Mesozoic-Cenozoic sedimentary rocks resulting in calcium bicarbonate-type water with low mineral content. The high water quality of the waterhead is deteriorated in the upper-middle part of the catchment due to: occurrence of evaporite-bearing geological formations, and the mining and industrial activities related to potash exploitation. As a result, an obvious increase in Na, K, Mg, Cl-, Br, Rb, and Sr concentrations is reported leading to a sodium (potassium) chloride water type. This saline hydrochemical fingerprint persists downstream. This important feature renders the low water quality of the Llobregat River to be adequate for drinking supply purposes. In addition, the industrial and residential activities, specially at the lower part of the catchment, increases P, B, Mn, Fe, Pb, Al, Cr, Co, Ni, Cu, Zn, As and Sb water concentrations.