A method was investigated for the determination of 4 phenols in water by three phase hollow fiber microextraction coupled with high performance liquid chromatography. Some factors affecting the extraction efficiency were optimized, such as the nature of organic solvent, the concentration of acceptor phase, the pH value of donor phase, extraction time, stirring rate and salt concentration. The optimized conditions were as follows: 1-octanol was used as the organic solvent, the concentration of NaOH solution as acceptor phase was 0.09 mol/L, the pH value of donor phase was 4, the extraction time was 40 min, the stirring rate was 600 r/min and the NaCI concentration was 100 g/L. Under the optimal conditions, the detection limits (S/N = 3) of phenol, 4-methylphenol, 2,4-dimethylphenol and 2-naphthol were 0.4, 0.4, 1.2 and 0.4 microg/L, and the enrichment factors were 111.6, 129.5, 71.0 and 175.6, respectively. The proposed method was applied for the determination of the 4 phenols in real environmental water samples and the spiked recoveries were in the range of 85.9%-119.0% at the spiked levels of 5 and 50 microg/L. The method is simple, rapid, accurate and suitable for the determination of phenols in water samples.