The molecularly imprinted bulk polymer with 2,4,6-trichlorophenol (2,4,6-TCP) as the template molecule and methylacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA) as functional monomer and the crosslinker, respectively, has been prepared and applied to the molecularly imprinted solid-phase extraction (MISPE) procedure for selective preconcentration of phenolic compounds from environmental water samples. Various parameters affecting the extraction efficiency of the polymer have been evaluated to optimize the selective preconcentration of the phenolic compounds from aqueous samples. The characteristics of the MISPE method were valided by HPLC. The recoveries ranged between 90% and 98% (RSD: 0.9-2.3%, n = 3) for tap water, between 85% and 105% (RSD: 2.6-4.9%, n = 3) for river water, between 78% and 98% (RSD: 2.6-5.4%, n = 3) for sewage water fortified with 0.4 mg L-1 of phenol, 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), pentachlorophenol (PCP). It was demonstrated that this MISPE-HPLC method could be applied to direct preconcentration and determination of phenolic compounds in environmental water samples. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.