Synthetic pyrethroids (SPs) are a group of hydrophobic compounds with significant aquatic toxicity. Their strong affinity to suspended solids and humic materials suggests that SPs in natural surface water are distributed in solid-adsorbed, dissolved organic matter (DOM)-adsorbed, and freely dissolved phases. The freely dissolved phase is of particular importance because of its mobility and bioavailability. In the present study, we used solid-phase microextraction to detect the freely dissolved phase, and we evaluated the phase distribution of bifenthrin and permethrin in stream and runoff waters. In stream water, most SPs were associated with the suspended solids and, to a lesser extent, with DOM. The freely dissolved phase contributed only 0.4% to 1.0%. In runoff effluents, the freely dissolved concentration was 10% to 27% of the overall concentration. The predominant partitioning into the adsorbed phases implies that the toxicity of SPs in surface water is reduced because of decreased bioavailability. This also suggests that monitoring protocols that do not selectively define the freely dissolved phase can lead to significant overestimation of toxicity or water-quality impacts by SPs.