The temporal dynamics of pesticide concentrations in streams remains poorly characterized in southwestern Ontario, a region of the province where land use is dominated by agriculture. Understanding the magnitude and duration of pulsed exposures to pesticides in these small streams is critical when estimating the risk of pesticides to these aquatic ecosystems. The present study investigated the application of a high-frequency water sampling approach paired with the collection of flow data to characterize the pulsed exposure of pesticides to small streams in southwestern Ontario. Six sites along 2 different streams with different magnitudes of agricultural land use in their upstream catchments were sampled using half-day composite samples from July to October 2018 and from May to September 2019. A total of 1043 samples were collected over the 2 yr, of which 210 were analyzed. Samples for analysis were chosen based on flow, water level, and precipitation data. Liquid and gas chromatography coupled with tandem mass spectrometry was used to measure >500 pesticides in each water sample. A total of 35 different compounds were detected over the 6 sampling sites. For pesticides that were detected in >10% of water samples above the method quantification limit, a deterministic risk assessment using water quality guidelines and a probabilistic risk assessment using species sensitivity distributions were performed. The calculated hazard quotients showed that 2,4-D, atrazine, metolachlor, and metribuzin exceeded a level of concern of 1 at the highest concentrations detected. In all cases, hazard concentrations that would be protective of 95% of species from the species sensitivity distributions were greater than the 95th centile of the environmental exposure distributions, meaning that the risk from the pesticides was low.