The bioavailability of polycyclic aromatic hydrocarbons (PAHs) to benthic organisms is complicated by the variety of ways that they are introduced to coastal waters (dissolved, as nonaqueous phase liquids, and tightly bound to soot, coal, tire rubber, and eroded shale). In order to better understand the controlling variables that affect chemical and biological availability of PAHs, a study was conducted in which three deposit-feeding infaunal benthic invertebrate species (Cirriformia grandis, Clymenella torquata, and Macoma balthica) were exposed to sediments amended with PAH-rich materials (coal dust, tire rubber, diesel soot, creosote, crude oil, and fuel oil). Lipid and organic carbon normalized bioaccumulation factors (BAFlocs) were calculated after 20 d of exposure and PAH bioavailability from the different treatments was assessed. Bioaccumulation of coal-derived PAHs usually was too low to be measured, though PAHs associated with soot and tire rubber showed significant accumulation in organism tissues. Polycyclic aromatic hydrocarbons from the fuel oil, creosote, and crude oil treatments were more bioavailable than PAHs bound in solid carbonaceous matrices (soot, coal, and tire rubber). Desorption of PAHs from the amended sediments into seawater also was measured using XAD resin. As was observed with bioaccumulation, PAHs in coal were desorbed the least; tire rubber and diesel soot were intermediate; and creosote, fuel oil, and crude oil desorbed to the greatest extent. In only one out of the three species evaluated was PAH bioaccumulation related to extent of desorption after 20 d. Decoupling between biological and chemical availability may be due to species-specific factors such as surfactant-mediated solubilization in the guts of some deposit-feeding organisms. A significant finding of this work was the demonstration that PAHs associated with soot and tire rubber in their native state (rather than experimentally added) are available to some benthic biota.