The pore size distribution (PSD) of adsorbents has been found to be an important factor that affects adsorption capacity for organic compounds; consequently, it should influence competitive adsorption in multisolute systems. This research was conducted to show howthe PSD of activated carbon affects the competition between natural organic matter (NOM) and the trace organic contaminant atrazine, with a primary emphasis on quantifying the pore blocking mechanism of NOM competition. Isotherm tests were performed for both atrazine and NOM from a groundwater on five powdered activated carbons (PACs) with widely different PSDs. The capacity for NOM correlated best with the surface area of pores in the diameter range of 15-50 A, although some NOM also adsorbed in the smaller pores as evidenced by a reduction in capacity for atrazine when NOM was present. Kinetic tests for atrazine on PACs with various levels of preadsorbed NOM showed that the magnitude of the pore blockage effect by NOM was lower for PACs with higher surface area of pores with diameter in the range of 15-50 A. Therefore increasing pores in the size range where NOM adsorb can reduce the extent of the pore blockage competitive effect on the target compound atrazine. The effect of PSD was further studied with a flow-through PAC-membrane hybrid watertreatment system, in which experimental results successfully verified model simulations by the COMPSORB model.