[Abstract] Stable or metastabie minerals are established for 381 sampling points from river water compositions for every spanish watershed aiong the years 1974-75, 1975-76, 1981-82, 1982-83 and 1983-84, as published by the spanish Department of Public Works. Phase diagrams for the systems SiO2-Al2O3-H2O, K2O-SiO2-Al2O3-H2O, Na2O-SiO2-Al2O3-H2O, MgO-SiO2-Al2O3-H2O, and CaO-SiO2-Al2O3-H2O, for 298 K and 1 atm. conditions, are used in order to determine the mineraiogical stability, and therefore neoformation trends. Stable and metastable phases were taken into account to draw the diagrams (Fernandez Marcos and Macias, 1987). The prevailing trend in the Peninsula, according to this method, is towards kaolinite neoformation. Nevertheless differences are observed between watersheds. So kaolinite is the only stable mineral neoformed in the North watersheds while there exist severa! stable minerals (kaolinite, mica, (kaolinite, mica, chlorite, pyrophillite) or metastable ones (smectite) in the Tajo, Guadiana, Guadalquivir, South, Jucar, Segura and East Pyrenees watersheds, depending on sampling point and date. Geographic distribution of different minerals is satisfactorily explained by taking into account: rainfall distribution, sileceous or calcareous nature of ground, and upper, medium or lower position in the river course.