Abstract: Sierra de Segura (Betic Cordillera), with a total area of over 3000km2, is the source of the two principal rivers in southern Spain, the Guadalquivir and the Segura. Due to the orographic effect of these mountains, precipitations are considerably more abundant than in nearby lowland areas, where the climate is semi-arid. Sierra de Segura is constituted of Mesozoic and Cenozoic sedimentary rocks, among which there are thick limestone–dolomitic formations which have given rise to extensive outcrops of permeable materials. In geomorphological terms, there is a large plateau intensively karstified that constitutes the main recharge area. Discharge takes place via a large number of springs, of which the 50 most important add up to a mean spring flow of about 13,500l/s. The active geochemical processes in aquifers of Sierra de Segura, with their corresponding time sequence, are: dissolution of CO2, dissolution of calcite, incongruent dissolution of dolomite, dedolomitization, exsolution of CO2, and precipitation of calcite. More evolved water has higher temperature, magnesium content and Mg/Ca ratio; therefore, these parameters can be utilised as indicators of the degree of hydrochemical evolution. In addition, a good correlation between water temperature and magnesium concentration (or Mg/Ca ratio) indicates that an increase in temperature accelerates the kinetics of the dissolution of dolomite. Finally, the distribution of the temperatures in the vadose zone, determined by atmospheric thermal gradient, implies an apparent stratification of the predominant hydrochemical processes and of the groundwater physical and chemical characteristics.