Improved approaches are needed to assess bioavailability of hydrophobic organic compounds in contaminated soils. Performance of thin-film solid-phase extraction (TF-SPE) using vials coated with ethylene vinyl acetate was compared to earthworm bioassay (Lumbricus terrestris). A DDT and dieldrin contaminated soil was amended with four organic carbon materials to assess the change in bioavailability. Addition of organic carbon significantly lowered bioavailability for all compounds except for 4,4′-DDT. Equilibrium concentrations of compounds in the polymer were correlated with uptake by earthworms after 48d exposure (R2 = 0.97; p < 0.001), indicating TF-SPE provided an accurate uptake simulation. Bioavailability of residues in soil was compared with a spiked soil aged for 90d in laboratory. Dieldrin and DDX were respectively 18% and 11% less bioavailable in contaminated soil relative to spiked soil despite >40yr of aging. Results show that TF-SPE can be useful in examining potential risks associated with contaminated soils and to test effectiveness of remediation efforts.