Passive sampling has been developed recently and is a useful sampling technique for the monitoring of aquatic environment. Several passive samplers have shown good performances for the determination of reliable estimates of different classes of micropollutants, with different physicochemical properties. In this study, we used the Stir Bar Sorptive Extraction (SBSE), a lab preparation technique for hydrophobic compounds, directly in river waters for the passive sampling of 16 pesticides (herein named “Passive SBSE”). In this study, we applied the Passive SBSE in two rivers of a small French vineyard watershed for periods of 7 days during two one-month field campaigns, and we determined the average concentrations of the target pesticides during the exposition periods. Results showed that the performances of the Passive SBSE were similar to those of active sampling techniques (grab and average automated samplings). Then ,we assessed the uncertainty of the passive sampling technique and the influence of experimental conditions on the accumulation of the target pesticides.