In this paper, the Multiple headspace solid-phase microextraction (MHS-SPME) principle and influencing factors of the technology are discussed in detail, and the advantages and disadvantages of the method are compared and analyzed. The applications of multiple headspace solid phase microextraction in food and agriculture fields are summarized. For example, the application in analysis of red wine, cheese, tomato and mushroom. The problems and development prospects of this method are discussed as well.