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Bioavailability is recognized as a useful technical standard for risk assessment and pollution rehabilitation. However, knowledge on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated site soils is still limited, especially concerning the influential mechanism. With an abundance of soil collections from nine industrial areas in China, the bioavailabilities, as conceptually defined as bioconcentration factors (BCFs) of PAHs were analyzed using biomimetic extraction of hydroxypropyl- β -cyclodextrin (HPCD). Apart from the total content of PAHs varying with the different pyrogenic sources, the BCFs were greatly dependent on the soil physicochemical properties from the spatial scale and inversely proportional to the number of rings. Pearson correlation analysis indicated a weak relationship between bioavailability and the soil dissolved organic matter (DOM), pH and particle size. To incorporate the soil physicochemical properties and structural characteristics of PAHs determined by density functional theory (DFT), the optimum model for bioavailability was developed for BCFs by partial least square (PLS) analysis. The PLS-derived model was shown to be predictive within the applicability domain (AD). The structural characteristics, e.g., molecular polarizability and frontier orbital energy level that favor the soil adsorption of PAH isomers via dispersion interactions, and electron exchanges were indicated to be more impactful on bioavailability than soil environmental factors. However, soil factors should not be neglected, because the pH, DOM, etc. were significantly influential. It makes sense that the higher DOM causes greater bioavailability via increasing the free-dissolved fractions of PAHs. Interestingly, the effect of pH on bioavailability was spectrally validated by excitation-emission matrix (EEM) fluorescence, showing that the interaction between DOM and pyrene strengthened the fluorescence quenching of chromophores with the decline in pH. [Display omitted] • Bioavailability of PAHs in contaminated site soils was determined by HPCD-extraction. • Bioavailability varied with soil heterogeneity and industrial activities. • A PLS-derived model was obtained and verified with great predictive performance. • Structural characteristics showed greater influence on bioavailability than soils. • The negative effect of soil pH was spectrally validated via the regulation of DOM binding. [ABSTRACT FROM AUTHOR]