In order to find out the distribution characteristics of BTEX in groundwater, which include Benzene, Toluene, Ethylbenzene, p-Xylene, m-Xylene, and o-Xylene, 82 groups of groundwater samples and 10 surface water samples collected from Guangzhou in Guangdong during 2005 to 2008 were tested by gas chromatography and mass spectrum(GC/MS). The result showed that the BTEX concentration in groundwater does not exceed the standard. The detection rate of BTEX is 14.63% in groundwater, and the total BTEX concentration is lower than 9.5 μg/L. Of 6 kinds of BTEX, toluene had the highest detection rate (12.20%) and detection value (9.5 μg/L), which was followed by Benzene, with the detection rate of 3.65%, and detection value of 4.9 μg/L respectively; most of samples with BTEX are distributed in Huangpu district, Baiyun district, Huadu district and other industrialized areas; this spatial distribution and urban distribution have obvious consistency. With economic development, plant expansion and population growth led to a large amount of waste water discharge, and infrastructure construction is lagging behind, indicating that rapid urbanization is a major driving force of BTEX in groundwater, and through the analysis of a typical area, it is found that benzene system surface water infiltration was an important source of BTEX in groundwater of Guangzhou.