The partitioning between solids and the aqueous phase largely controls the fate of PAH compounds in biological treatment. The prediction of PAH sorption behaviour into activated sludge was investigated here. The suitability of a three-compartment model to describe partitioning in such a complex matrix was first evaluated by adding increasing quantities of dissolved and colloidal matter (DCM) (from 0 to 34.9% of the total matter). In a range of DCM concentrations varying from 0 to 1.4 g L-1, the PAH aqueous fraction, including both freely dissolved and sorbed to DCM molecules, increased from 9.9% to 33% for naphthalene (the most soluble PAH) and from 0.29% to 13.3% for indeno(1,2,3,c,d)pyrene (the least soluble PAH tested). The sorption of PAHs on dissolved and colloidal matter (DCM) was assessed by determining two partitioning constants (K-PART and K-DCM) for the 16 PAHs listed by the US EPA. New experiments were carried out for model validation and show that the model properly predicts the PAH partitioning following sludge disintegration by sonication.