Ambient ionization mass spectrometry plays a pivotal role in the analysis of complex samples owing to the features of no sample pretreatment,easy to use and high efficiency.However,this methodology would result in a simultaneous ionization of sample matrices and target analytes,and the analysis sensitivity of mass spectrometry would be greatly reduced.Solid phase microextraction has been demonstrated to be an effective avenue either to enrich target analytes or to remove matrices from complex samples prior to mass spectrometric analysis,which significantly improves the limit-of-detection of determined compounds.In this work,recent advances in solid phase microextraction techniques,either being coupled directly to ambient ionization sources or capable of in situ ionization of target analytes,are reviewed,and their principles and applications to the analysis of complex samples are summarized.Moreover,the perspectives of solid phase microextraction direct mass spectrometric analysis have been exemplified based on the current development.