Aqueous sampling rates for 25 pharmaceuticals and personal care products (PPCPs) were determined on the commercially available passive Polar Organic Chemical Integrative Sampler (POCIS). To date, POCIS calibration has only been carried out for a handful of compounds. Uptake rates were 0.040 to 2.462 L/d under conditions of flowing water; quiescent conditions resulted in uptake rates between 0.016 and 0.223 L/d. The uptake of many PPCPs appears to be boundary-layer controlled, as indicated by higher sampling rates under flowing conditions. Sampling rates were corrected for analyte dissipation rates, and some correlations with octanol–water partition coefficients were noted. Field deployments of POCIS in wastewater effluent and surface waters had time-weighted average concentrations derived from laboratory calibrations that were consistent with regular grab samples. This work indicates that POCIS can be used as a quantitative tool for measuring PPCPs in the aquatic environment.