Abstract: Some application of headspace analysis of volatile compounds in complex materials are reviewed. Three main modes of headspace analysis are introduced. The basic principle of three main headspace analysis modes and the optimization of static headspace system conditions are discussed. The research application and progress of various application are reviewed, such as analysis of organic volatile compounds in biological fluids and materials, the determination of volatile impurities in drug pharmaceutical materials and substance, residual solvents and volatile organic compounds in polymer and resin, environmental analysis and research of essential oils.