In the present study, the relationship between bioavailability of polycyclic aromatic hydrocarbons (PAHs) to benthic amphipods and the PAH desorption kinetics was examined. To that end, field-contaminated sediment was treated in three different ways. One subsample had no addition of PAHs and contained native PAHs only. To a second subsample, six PAHs (phenanthrene, fluoranthene, anthracene, pyrene, benzo[b]fluoranthene, and benzo[k]fluoranthene) were added in the laboratory. Two of the PAHs were added at higher concentrations to a third subsample, serving as a control for concentration-dependent uptake. Marine amphipods (Corophium volutator) were exposed to the three subsamples for a maximum of 25 d and were subsequently analyzed. Desorption kinetics were determined for both the lab-contaminated and the native PAHs. The biota-to-sediment accumulation factor (BSAF) values of the individual native and lab-contaminated PAHs correlated well with the rapidly desorbing fraction (R2 = 0.76). The BSAFs were 1.4 to 3.3 higher for the lab-contaminated PAHs compared with the native PAHs, while the difference between the rapidly desorbing fractions was a factor of 1.1 to 1.8. The BSAFs of the lab-contaminated PAHs in the second and third subsample were equal, indicating concentration-independent accumulation. The results suggest that lab-contaminated PAHs are more available to amphipods than native PAHs and that differences in bioavailability of lab-contaminated and native PAHs to marine amphipods are related to differences in desorption behavior.