The effects of pesticide exposure on human health have been demonstrated by numerous epidemiological studies. However, these studies face challenges in identifying the pesticides associated with specific diseases due to the wide variety of products available and the difficulty respondents have in recalling details. To identify the pesticides to which populations are exposed, this report presents a method based on cross-referencing crop-exposure matrices (CEM) with agricultural census data (AC). Two approaches were used to define indicators of pesticide exposure, linked to their agricultural use, at the cantonal level to describe: (i) on the one hand, environmental exposure affecting the general population, and (ii) on the other hand, worker exposure. The available CEMs provide a historical and geographical description of exposure to pesticide subgroups (fungicides, herbicides, insecticides), chemical families, and active ingredients across four crops (straw cereals, corn, potatoes, and grapevines), covering 75% of agricultural land (excluding pastures and fallow land). These were combined with data from the RA, which describes agricultural holdings in metropolitan France. Environmental exposure was determined based on the agricultural land areas of the cantons, and occupational exposure based on the crops grown and their combination within the canton’s agricultural holdings. The indicators defined for each type of exposure are: probability of exposure, average number of annual applications, and amount applied. They were calculated for the 3 pesticide subgroups, 109 chemical families, and 197 active ingredients for each year from 1979 to 2010, and for each canton in metropolitan France (N = 3,689). The results for the chemical family of aryloxy acids (herbicides) and for the active ingredient 2,4-D are presented for illustration. They show trends over time and a heterogeneous distribution across the territory. This method, which uses reference data determined by experts, was applied to all of metropolitan France over a period of thirty-two years. It can be used in epidemiological studies to identify geographic areas with varying levels of exposure to certain pesticides and to examine the ecological association between these indicators and disease incidence.