Since the discovery of Grignard reagents, the synthesis of highly functionalized organomagnesium compounds has been hot but difficult project.In the presence of LiCl, a series of polyfunctional Grignard reagents were successfully prepared by Knochel group via direct oxidative addition of magnesium to organic halides, halogen-magnesium exchange reaction, or direct magnesiation of C-H bond.In the presence of LiCl, the issue of functional group compatibilities was addressed and the reactivity was also enhanced.Consequently, the applications of Grignard reagents in synthetic chemistry were greatly expanded.The limitations and potential research areas for LiCl-promoted synthesis of Grignard reagents are also discussed.