There is a more diverse set of substances that may cause special odors in water bodies, so that it is difficult to analyze many factors that will make an increasing impact on the social and economic environment, thus seriously hobbling the people's demand for better life. Against this backdrop, how to quickly and accurately test smelly substances in water, ensure the safety of water areas, and make up for the gaps of the existing technologies has become a worthy focus of concern. In this paper, the headspace solid phase microextraction and the Gas Chromatography/Mass Spectrometry (GC/MS) are incorporated to analyze the smelly substances, in order to determine the optimal extraction and experiment conditions. In this way, the method has been proven to be effective in determining the smelly substances. Study results show that the accuracy every time reaches above 93%, which suggests that the test and identification technology for smelly substances is feasible. For example, test odorous substances in Taihu Lake, it provides the clues to deodorizing water and ensure the water safety of Taihu Lake and other water areas.