A simple analysis of chlorophenols (2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol) and phenol was accomplished by coupling a pressurized CEC with amperometric detection (AD). Efficient and reproducible separation of these compounds was achieved within 9 min on a capillary monolithic stationary phase bonded with octadecyl ligands and sulfonate groups, where the selectivity and the retention of analytes can be functionally controlled by optimizing experimental variables, including organic modifier content, mobile phase pH, ionic strength, working electrode potential, separation voltage, and supplementary pressure. A mixed-mode retention mechanism consisting of reverse-phase chromatographic partition, electrostatic repulsion, and electrophoresis is considered to play roles in the separation. The use of ACN-based media seems effectual in preventing the unfavorable irreversible adsorption on both wall and electrode, and offer higher sensitivity and less electrode fouling in AD of phenols. The LODs were in the range from 0.02 to 0.2 g/mL with a wide linear dynamic range of 5000-fold, while the peak area precision ranged from 3.2 to 7.5%. The feasibility of using this method in real analysis was evaluated by recovery estimates and comparative experiment on spiked tap water samples. Good recoveries of 80-110% were achieved. Additionally, a paired t-test was used to correlate the two methods.