A new analytical approach to determine the speciation of hydrophobic organic analytes is presented. The freely dissolved concentration in a sample is controlled by passive dosing from silicone (poly(dimethylsiloxane)), and the total sample concentration at equilibrium is measured. The free fraction is determined as the ratio between measured concentrations in pure water and sample. C-14-labeled fluoranthene served as model analyte, and total sample concentrations were easily measured by liquid scintillation counting. The method was applied to surface water, stormwater runoff, and wastewater. In the untreated wastewater, 61% of the fluoranthene was bound to suspended solids, 28% was associated to dissolved organic matter, and 11% was freely dissolved, while in treated wastewater, the speciation was 16% bound to suspended solids, 4% bound to dissolved organic matter, and 80% freely dissolved. The free fraction in roof runoff (85%) and surface water (91%) was markedly higher than in runoff from paved areas, which ranged from 27 to 36%. A log K-DOC value of 5.26 was determined for Aldrich humic acid, which agrees well with reported values obtained by fluorescence quenching and solid phase microextraction (SPME). This analytical approach combines simplicity with high precision, and it does not require any phase separation steps.