A new method was developed for the determination of trace compounds in water samples using ultrasonic-enhanced hollow fiber liquid-phase microextraction (U-HF-LPME). The ultrasonic radiation, which produces mechanical vibration and ultrasonic cavitation, could be used for accelerating the diffusion mass transfer process. Thus, ultrasonic was introduced into the HF-LPME procedure to enhance the mass-transfer rate during the aqueous and extraction solvent phases. Experimental parameters such as the extraction solvent, the extraction time, the ultrasonic frequency and power, the extractant volume, and ionic strength of the sample were assessed and optimized. Under optimal conditions, HF-LPME was achieved within 10 min. The high enrichment factor in the range of 120-666 and a good relative recovery in the range of 97-103% were evaluated with the relative standard deviations (RSDs, n = 5) of 0.3-7.0%. The limit of detection was in the range of 0.8-3.0 µg/L. The method was applied to the analysis of groundwater, lake water, and seawater. The results showed that the method can determine trace benzene derivatives in real samples with RSD values of 1.1-4.2%. The results demonstrated that U-HF- LPME is a rapid, accurate, and effective sample preparation method, and could be successfully applied for the determination of trace compounds in analytical chemistry.