Abstract: The purge and trap gas chromatography-mass spectrometry(GC-MS) is established for the determination of 60 volatile organic compounds (VOC) in groundwater of enterprise land of key industries. The purge and trap conditions are optimized by selecting Watsons double-distilled water as blank water, ion and full scanning alternating mode for qualitative-quantitative analysis and determination of types and dosages of protective agent. The detection limit of the method is 0.3-1.2 μg/L, with the linear range of 0-250 μg/L, and correlation coefficient(R²) of 0.9907-0.9999. The spiked average recovery of three different concentrations are 87.2%-117%, with the relative standard deviation of 1.7%-9.7%, which is better than the quality control requirements of "Technical Specifications on Quality Assurance and Control of Survey for Enterprise Land of Key Industries (Trial)" for VOCs in groundwater. The method adds test types of VOCs, with wide linear range and high sensitivity, suitable for rapid batch analysis of 60 VOCs in groundwater of enterprise land of various key industries.