In this study, we investigated the effect of freeze-thaw cycles of sewage sludge (SSL)- and willow-derived biochars obtained at different temperatures on their physicochemical properties and total (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) content. In our research, we showed that the fate of Ctot PAHs depended on the type of SSL and may differ, which is determined mainly by the properties of the feedstock. The properties affect low-temperature SSL-derived biochars (500 °C) especially, in which the interactions based on π-π bonds between the PAHs and matrix during aging were weakened by newly created functional groups on the biochar surface. Additionally, the removal of ash or biochar particle fragmentation during aging increased the availability of solvent non-extractable PAHs, which resulted in an increase in the content of high molecular weight Ctot PAHs after aging. In turn, the Σ16 Cfree PAHs in biochars gradually decreased with their progressive surface functionalization, increase in specific surface area and pore volume and generally were independed on properties of feedstock and biochar. The obtained results evidence that the environmental risk associated with the use of SSL as a feedstock for biochar production is similar to or even lower than in the case when willow is used and depending on SSL type, the potential risk may be reduced or increased for low-temperature biochars.