An ultrasound-assisted headspace liquid microextraction method is presented. The organic solvent droplet is suspended at the bottom of a polychloroprene rubber tube. More extractant can be held and the stability of microdrop is better than by using a syringe needle so that extraction aided by ultrasonication can be carried out. Compared with traditional methods, the extraction efficiency is about ten times higher. The method has been used to determine phenols in real water samples, and good recoveries were obtained. It is a promising alternative for analyzing volatile or semivolatile pollutants in environmental samples due to its simplicity, rapidity and stability.