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Polydopamine (PDA)-coated magnetic multiwalled carbon nanotube (M-MWCNT) composites were synthesized in two facile preparation steps, and were used as adsorbents for magnetic solid-phase extraction (MSPE) coupled with high-performance liquid chromatography (HPLC) for simultaneous extraction, enrichment and determination of five kinds of typical chlorophenols (CPs) in water samples. The as-prepared magnetic composites showed excellent magnetic properties and high thermal stability. Various main parameters influencing the extraction efficiency of MSPE were systematically investigated. Under the optimized MSPE–HPLC conditions, a high enrichment factor (EF) was obtained in the range of 85–112 for 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,6-dichlorophenol (2,6-DCP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP). Good linearity was obtained in the range of 2.0–200 μg L−1 for 2-CP and 4-CP and 1.0–200 μg L−1 for 2,6-DCP, 2,4-DCP and 2,4,6-TCP, with a correlation coefficient (R2) higher than 0.9964. The limits of detection (LODs) and the limits of quantification (LOQs) were in the range of 0.10–0.31 μg L−1 and 0.35–1.03 μg L−1, respectively. The intraday and interday precisions evaluated using relative standard deviation (RSD) values were in the range of 1.05–2.25% and 1.88–2.83%, respectively. The validated MSPE–HPLC method was also successfully applied to analyze five kinds of CPs in tap water, lake water, river water and seawater samples, and satisfactory recoveries were obtained in the range of 76.87–106.5% with RSDs of 1.64–6.78%. [ABSTRACT FROM AUTHOR]