Urinalysis of toluene is important to monitor workers occupationally exposed to toluene as well as in the diagnosis of some diseases related to chronic human exposure. Studies were carried out to establish the best extraction conditions for the method, taking into account the various factors that affect the technique, suchas heating time, heating temperature, and the effect of salt addition. This work shows a sensitive, simple,and rapid static headspace-gas chromatographic procedure for the quantitative determination of toluene in urine. The limit of detection for toluene is 0.029 µg/L, with a standard deviation of less than 6%. Precisions (%RSD) for toluene at different levels were less than 21%. Recoveries for toluene ranged from 80 to 110%. Determination of Toluene in Urine using Headspace/Gas-Chromatography- Mass Spectrometry has thesensitivity, repeatability, and recovery requirements of AOAC.