Time of flight mass spectrometry (TOF-MS) has been widely applied in food, biological medicine, environmental monitoring for its great precision, wide range of detection and high speed of analysis. TOF-MS with various techniques in tandem plays an important role in the structure identification of polyphenols. In this review, it was outlined the application of time of flight mass spectrometry in the structure identification of plant polyphenols to provide some references for the study of plant polyphenol.