A large series of data on dissolved antimony concentrations (900 values) from the hydrological network of Canton Geneva, Switzerland, has been statistically analysed. Data were collected from 90 sampling sites over 12 years. The watercourses surveyed (178 km) accounted for 73% of the total network. Previous studies have classified these rivers as belonging to three clearly-differentiated lithogenic zones: Alps (rivers draining crystalline regions), Jura (rivers draining carbonate-rich zones) and Plain (rivers draining molasses derived from the Alps). Antimony concentrations in the different river waters have been found to be significantly dependent on the geological characteristics of the drainage basins (median values: 0.13, 0.08 and 0.16 µg L−1 for Alps, Jura and Plain, respectively). For antimony, it is thus possible to define background levels of the element adapted to the lithogenic characteristics for a system of interest. Since establishing background levels is an unavoidable preliminary step in any study aiming to identify and evaluate the various sources of pollution, the behaviour described here has undeniable implications for environmental surveys.