BF3 center dot OEt2, as a typical Lewis acid catalyst with excellent catalytic capacity, plays an important role in many reactions, such as coupling, cyclization and rearrangement, and it is widely used in the synthesis of natural products, pharmaceutical molecules and other functional molecules. Interestingly, in the presence of water, BF3 center dot OEt2 can be combined with water to form Bronsted acid, which can also promote the coupling, addition, and other reactions. At the same time, BF3 center dot OEt2 is not only limited to be a catalyst, but also can be used as a synthon to mildly construct compounds containing B, F and BF2 structure molecules, which plays an important role in the field of catalytic ligand and fluorescence molecules. Based on various catalytic reaction types using BF3 center dot OEt2 and its different applications as a synthon, the research progress on the application of BF3 center dot OEt2 in organic synthesis in recent years is reviewed. Looking forward to the future, with the in-depth study of BF3 center dot OEt2, there will be more understanding of its performance and application, it is possible to develop more surprising catalytic systems and synthetic applications.