A previous study on mobilization of organochlorine pesticides (OCPs) in contaminated soils from the field revealed that the total amount of OCPs measured in digestive fluid and chyme of an in vitro gastrointestinal model was higher than the quantity directly extracted using a solvent extraction without digestion, providing a clue that the bound residue of OCPs might be mobilized. This hypothesis was tested in this study for both OCPs and polycyclic aromatic hydrocarbons (PAHs). Three contaminated surface soil samples with different organic carbon (OC) contents were collected from the field, and extracted with a solvent with and without digestion in an in vitro gastrointestinal model. It was found that bound residues of OCPs and PAHs were mobilized to a certain extent during digestion. The ratios of the mobilized bound residues over the total quantities extracted after digestion (R(b)) varied from 0 to 0.96 for individual compounds. The R(b) was positively correlated with OC content. Among the five constitutes of digestive juice, bile salt was the only one that served to mobilize the bound residues and the extractability of bile salt was constant over a concentration range from 2 to 20 mg/mL. The mobilization process followed typical first-order kinetics. The calculated rate constants suggest that mobilization was fast and 90% of extracted bound residues of OCPs and PAHs were mobilized within 2.4 and 4.8 h, respectively.