Abstract: Comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-qMS) with new solid state modulation technique was applied to qualitative analysis of industrial waste water and a total of 162 organic pollutants were identified. As shown by the results, the organic pollutants were mainly composed of benzenes and naphthalenes. The compounds with similar structure exhibited highly ordered distribution in the GC×GC chromatogram, giving feasibility for clustering analysis of these compounds. With larger capacity for chromatographic peaks, higher resolution and sensitivity, GC×GC-qMS showed its merits to be an accurate and reliable method for analysis of complex samples.