Three classification techniques (loading and score projections based on principal components analysis (PCA), cluster analysis (CA) and self-organizing maps (SOM)) were applied to a large environmental data set of chemical indicators of river water quality. The study was carried out by using long-term water quality monitoring data. The advantages of SOM algorithm and its classification and visualization ability for large environmental data sets are stressed. The results obtained allowed detecting natural clusters of monitoring locations with similar water quality type and identifying important discriminant variables responsible for the clustering. SOM clustering allows simultaneous observation of both spatial and temporal changes in water quality. The chemometric approach revealed different patterns of monitoring sites conditionally named "tributary", "urban", "rural" or "background". This objective separation could lead to an optimization of river monitoring nets and to a better tracing natural and anthropogenic changes along the river stream.