In this work, adsorption behaviors of pyrene (PYR), fluoranthene (FLT), phenanthrene (PHE), and fluorene (FLU) on the coordination cluster [Zn-5(H2Ln)(6)](-)(NO3)(4)]center dot 8H(2)O center dot 2CH(3)OH (Zn-5) were studied. The adsorption mechanism and spectrum analyses revealed that the synergistic effect of hydrophobic interaction, pi-pi stacking, and N-H center dot center dot center dot pi interaction played a crucial role during the adsorption process. The maximum adsorption capacities of PYR, FLT, PHE, and FLU were 406.4, 399.7, 153.7, and 114.3 mg g(-1), respectively, resulting from the Langmuir isotherm model. Quick removal of PYR and FLT was found in kinetic experiments with the adsorption equilibrium being reached within 1 min. Competitive adsorption indicated that the adsorption sites for PYR, FLT, PHE, and FLU on Zn-5 were identical, and synergistic effects also existed in the adsorption process. Therefore, Zn-5 has the potential to be used as an adsorbent in the field of wastewater treatment.