Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated as surrogates to estimate bioavailability of polychlorinated biphenyls (PCBs) from field-contaminated sediment. Aroclor 1254 was the primary contaminant found in sediment from Crab Orchard Lake in Marion, Illinois, USA, and a total of 18 PCB congeners were selected for study. Bioaccumulation was determined by exposing the freshwater oligochaete, Lumbriculus variegatus, to the sediment for 28 d. Differences in the rapidly desorbing fraction of PCBs and fraction desorbed within 6 h, defined by Tenax extraction, accounted for 39 and 31% of the differences among biota-sediment accumulation factor values, respectively. A better relationship (r2 = 0.95) was found between the oligochaete PCB body residues and the concentration of PCBs in the rapidly desorbing fraction of sediment. The degree of chlorination and planarity of the PCB congeners affected both desorption and bioaccumulation. The higher chlorine substituted and planar PCBs showed less chemical and biological availability, due to their stronger sorption to sediment, compared to the lower chlorinated and nonplanar PCBs. Accumulation of PCBs by L. variegatus correlated well (r2 = 0.88) with matrix-SPME fiber concentrations. The ratio of measured body residue to estimated body residue from the pore water concentration measured by matrix-SPME ranged from 0.4 to 1.3 with an average of 0.9. Overall, both Tenax and matrix-SPME approaches were useful surrogates of bioaccumulation for a field-contaminated sediment.