The effects of polyvalent metal cations on pyrene binding to hydrophobic acid and neutral fractions (HoA and HoN, respectively) of dissolved organic matter (DOM) were elucidated. The DOM was isolated from sewage sludge; pyrene binding was estimated from fluorescence measurements. Isotherms of pyrene binding to both fractions were nonlinear. Pyrene binding was higher for HoN due to the combined effect of greater hydrophobicity, aromaticity and the large molecular size of this fraction relative to HoA. The complexation of HoA with Cu2+, Al3+, and Fe3+ increased the binding of pyrene only when the HoA was equilibrated with polyvalent cations before pyrene was added. The maximal increase in pyrene binding to HoA was 56%, 64%, and 118% when pre-equilibrated with Cu2+, Fe3+, and Al3+, respectively. Pyrene binding to HoN was not affected by the presence of metal cations. HoA complexation with metal cations increased the apparent molecular size of this fraction. We suggest that the presence of metal cations induces the formation of pseudomicelles, which are more efficient in binding pyrene than the low-molecular-weight components. Our results demonstrate that HoA and HoN components can significantly affect the transport of organic contaminants in soils irrigated with treated wastewater or amended with sewage sludge.