The serum pesticides analyzed in this report were selected as part of the prioritization process initiated for the development of the national biomonitoring program. The Laboratory for Environmental and Health Research (Leres) and Santé publique France have signed a research and development contract for the analytical development and quantification of these substances. Little exposure data is available in the scientific literature on the pesticides we sought to measure: amitraz, fipronil, methomyl, bromoxynil, and carbendazim. Once the analytical developments were completed by Leres, an initial series of analyses helped consolidate the list of metabolites and substances for which results could be interpreted: these were 5-HBC (a metabolite of carbendazim and benomyl), methomyl, bromoxynil, fipronil, and its two metabolites: fipronil-desulfinyl and fipronil-sulfone. In France, there are no data on exposure levels to these pesticides in the general population. The Esteban study provided the first description of the distribution of serum levels of these pesticides or their metabolites among adults aged 18 to 74 living in metropolitan France, based on a sample of 1,000 adults. The sample of children in the Esteban study could not be included in this analysis due to an insufficient amount of serum required for this test. Among the pesticides or their serum metabolites analyzed in this report, only bromoxynil was quantified in all adults who had a sufficient serum volume for this assay. One of the two metabolites of fipronil, fipronil-sulfone, was also quantified in more than half of the population. The other pesticides or metabolites were rarely or never quantified but were no longer authorized (for phytopharmaceutical use) in France between 2014 and 2016, the period of the Esteban survey. At that time, according to regulations, only bromoxynil and fipronil were still authorized for this use. Exposure determinants could only be investigated for bromoxynil, the only substance quantified in more than 60% of the sample. This investigation revealed associations between impregnation and the residential environment, the season of blood collection, and the consumption of vegetables from one’s own garden (hereinafter referred to as vegetable self-consumption). Repeated measurement of fipronil and its metabolites, as well as bromoxynil, in future biomonitoring studies could help determine whether the ban on these substances for phytopharmaceutical use has had an impact on the trends in measured levels among the adult population aged 18 to 74 living in metropolitan France.