Rainfall-triggered runoff is a major driver of pesticide input in streams. Only few studies have examined the suitability of passive sampling to quantify such episodic exposures. In this study, we used Empore™ styrene-divinylbenzene reverse phase sulfonated disks (SDB disks) and event-driven water samples (EDS) to assess exposure to 15 fungicides and 4 insecticides in 17 streams in a German vineyard area during 4 rainfall events. We also conducted a microcosm experiment to determine the SDB-disk sampling rates and provide a free-software solution to derive sampling rates under time-variable exposure. Sampling rates ranged from 0.26 to 0.77 L d⁻¹ and time-weighted average (TWA) concentrations from 0.05 to 2.11 μg/L. The 2 sampling systems were in good agreement and EDS exceeded TWA concentrations on average by a factor of 3. Our study demonstrates that passive sampling is suitable to quantify episodic exposures from polar organic pesticides.