Hybrid polycation-clay composites, based on methylated poly vinylpyridinium, were optimized as sorbents for secondary effluent organic matter (EfOM) including emerging micropollutants. Composite structure was tuned by solution ionic strength and characterized by zeta potential, FTIR, X-ray diffraction, and thermal gravimetric analyses. An increase in ionic strength induced a transition from a train to a loops and tails configuration, accompanied by greater polycation adsorption. Composite charge reversal (zeta potential -18 to 45 mV) increased the adsorption of EfOM and humic acid (HA), moderately and sharply, respectively, suggesting electrostatic and also nonspecific interactions with EfOM. Filtration of EfOM by columns of positively charged composites was superior to that of granular activated carbon (GAC). The overall removal of EfOM was most efficient by the composite with a train configuration. Whereas a composite with a loops and tails configuration was beneficial for the removal of the anionic micropollutants diclofenac, gemfibrozil and ibuprofen from EfOM. These new findings suggest that the loops and tails may offer unique binding sites for small micropollutants which are overseen by the bulk EfOM. Furthermore, they may explain our previous observations that in the presence of dissolved organic matter, micropollutant filtration by GAC columns was reduced, while their filtration by composite columns remained high.