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Traditional grab sampling (GS) used widely in the study of water quality has been found lacking in spatial and temporal resolution for pesticide residue monitoring in stream water. The objectives of this article are to present a hydrograph-based sampling approach and compare it with traditional GS according to sensitivity at temporal and spatial scales and maximum concentrations of pesticide residues detected in-stream. Data collected from streams receiving water from three nested watersheds located in northwestern New Brunswick, Canada, were used in this study. The results showed that the hydrograph-based sampling method detected 20 to 30 % more pesticide cases than GS for rainfall events causing runoff. Grab sampling significantly underestimated average concentrations of pesticide residues by 50 % and maximum concentrations by 1 to 3 orders of magnitude. Using a modified sampler design, the spatial and temporal variability of pesticide residues was more accurately captured by hydrograph-based sampling, and therefore its use in monitoring programs is recommended.