To assess the exposure to polycyclic aromatic hydrocarbons (PAHs) it is important to understand the binding mechanisms between specific soil constituents and the organic pollutant. In this study, sorptive bioaccessibility extraction (SBE) was applied to quantify the accessible PAH fraction in industrially contaminated soil with and without passive dosing of a competitive sorbate. SBE experiments revealed an accessible PAH fraction of 41 ± 1% (∑16 US EPA PAHs + 5 further PAHs). The passive dosing of toluene below its saturation level revealed competitive binding and resulted in an average increase of the accessible fraction to 49 ± 2%, whereby primarily the accessibility of higher molecular weight PAHs (log Kow > 6) was affected. Competitive binding was verified using the same soil with only desorption-resistant PAHs present. In this experiment, passive dosing of toluene resulted in desorption of 13 ± 0.4% PAH. We explain increased PAH desorption after addition of toluene by competitive adsorption to high-affinity sorption sites while acknowledging that toluene could additionally have increased PAH mobility within the soil matrix. Findings suggest that the presence of copollutants at contaminated sites deserves specific considerations as these may increase accessibility and thereby exposure and mobility of PAHs.