Objective A mixed-mode high performance liquid chromatography method was established for the determination of polycyclic aromatic hydrocarbons in water，especially for the determination of phenanthrene，fluorene，fluoranthene and acenaphenene by using a new stationary phase material（Sil-VMB-VSS）. Methods Chromatographic conditions: the stationary phase was filled with synthetic Sil-VMB-VSS，and the mobile phase was acetonitrile/ultrapure water（ 1:1）. The detection wavelength was 254 nm，the flow rate was 1.0 mL/min，the column temperature was 30℃，and the injection volume was 10 μL. Results The new column showed good linearity（R2 > 0.999）in the range of 0.25 ~ 10 μg/mL，0.025 ~ 1 μg/mL，1 ~ 50 μg/mL，0.1 ~ 10 μg/mL for the standard analytes of acenaphthylene，phenanthrene， fluoranthene and fluorene during this experiment，and the method had excellent precision and accuracy. The average recovery rate of fluorene solution with concentration of 5 μg/mL in water was 100.10%，which was in accordance with the requirements of the assay，and the recovery rate was measured 3 times. In addition，the recovery of acenaphthylene was also in accordance with the requirements. Conclusion The novel mixed-mode chromatographic column was sensitive to the detection of fluorene and acenaphthylene in water，which provided a new tool for the detection of environmental pollutants.