Conditions of the preconcentration of phenol on a microcolumn filled with MN-200 hypercrosslinked polystyrene were determined using the linear sorption dynamics model. Conditions of the on-line determination of phenol and its chloro derivatives by reversed-phase high-performance liquid chromatography with amperometric detection were optimized. The detection limit of phenol and chlorophenols for preconcentration from 30 mL of a sample was 3 and 15 ng/L, respectively. The proposed procedure was used for the determination of phenols in tap and river water.