Abstract: The microstructure of graphene plays an important role in its tribological properties, which is closely related to its synthesis method. Therefore, it is of great significance to clarify the relationship between graphene synthetic methods, microstructure control strategies, tribological properties and lubrication mechanisms for the development of high-performance graphene lubricant additives. Focusing on the synthesis and structural control of graphene lubricant additives, this article reviews a variety of synthetic methods for adjusting the microstructure of graphene, and summarizes the synthetic strategies for stable dispersion as well as the effects of microstructures on tribological properties. In addition, the microstructure evolution and the lubrication mechanisms of graphene are discussed. At last, the problems and the future trend of graphene as a high-performance lubricant additive are pointed out.