A poly(4-vinylpridine-co-ethylene glycol dimethacrylate) monolith was synthesized in a capillary and constructed as a concentrator for the in-line polymeric monolith microextraction coupling with capillary electrophoresis. The integrated system was then used for the simultaneous determination of five trace phenols (2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2-chlorophenol, and 2,4-dichlorophenol) in water samples. The experimental parameters for in-line solid-phase extraction, such as composition and volume of the elution plug, pH of sample solution, and the time for sample loading were optimized. The sensitivity for the mixture of phenols (2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2-chlorophenol, and 2,4-dichlorophenol) enhanced to 6152222 folds at the optimum condition was compared to the sensitivity for a normal hydrodynamic injection in capillary electrophoresis. Linearity ranged from concentration of 10500 ng mL-1(R2 > 0.999) for all five phenols with the detection limits of 1.33.3 ng mL-1. In tap, snow and Yangtze River water spiked with 20 ng mL-1 and 200 ng mL-1, respectively, the recoveries of 84105% were obtained. It has been demonstrated that this work has great potential for the analysis of phenols in genuine water samples.