Establishing determination system with solid-phase extraction and gas chromatography mass spectrometry （GC-MS） for application of the determination of phthalatic acid esters （PAEs） in Pearl River of Guangzhou section. Conditions of solid phase extraction were optimized by the type of eluent, pH value of water sample and volume of eluent, GC-MS was used to quantitate and analyze 4 kinds of target materials, such as dimethyl phthalate （DMP）, diethyl phthalate （DEP）, dibutyl phthalate （DBP）, diethylhexyl phthalate （DEHP）. The results showed that, when the pH value of water sample was 2. 0, and 4 mL V （ methylene chloride） ： V （ ethyl acetate ） = 1 ： 1 was used as the eluent, the recovery rate among 4 kinds of phthalic acid esters were 65.12% - 108.86% ; The detection limit ranges were from 0. 05 to 0. 45 μg/L, the average recovery was 86. 11% - 86. 11% , and relative standard deviation was 1.77% -4. 42%. This method is suitable for determining the content of phthalates in water for the advantages of convenience, fast and accuracy.