Abstract Groundwater of the unconfined Chalk aquifer in Champagne-Ardenne (NE France) is contaminated by perchlorate ( ClO 4 − ), a persistent water-soluble anion. The Chalk aquifer is a crucial water resource of the region, with complex hydraulic properties. The presence of ClO 4 − is of concern due to its potential adverse human health effects. In France, three sources of ClO 4 − contamination are suspected: industrial, military and agricultural. Both a comprehensive understanding of hydrogeological characteristics of the aquifer, and a sound knowledge of sources and behaviour of ClO 4 − in groundwater are required to allow the sustainable use of this groundwater resource. From data acquired during hydrogeological, geochemical, isotopic ( ClO 4 − ) and groundwater age (CFCs and SF 6 ) studies, and historical investigations in a study area located east of Reims, a conceptual model of Chalk aquifer function and ClO 4 − transfer has been established. High spatio-temporal heterogeneities in the unconfined Chalk aquifer are discussed. Different correlations between ClO 4 − , major ions and groundwater-level fluctuations are shown and interpreted, highlighting main factors governing the Chalk groundwater geochemistry and ClO 4 − transfer mechanisms, including water-level fluctuation, groundwater residence time, thickness of the unsaturated zone, superficial formations, distribution of fissure networks, aquifer–river relationships, origin and location of ClO 4 − in soil and human activity.