Graphene, graphene oxide and their composites have shown great potential in the field of advanced protective coating barriers, owing to their impermeability to oxygen and moisture, resistance to fouling species and antibacterial properties. In this chapter, we highlight the recent progress on the barrier materials based on graphene-related membranes. The fundamental theories are introduced, and the experimental performances as gas barriers, anticorrosion and antifouling coatings, and metal diffusion barriers in microelectronics are summarized. The industrialization of graphene-related coatings can be foreseen. This review will inspire the further developments of graphene-related protective coatings and urge their practical applications in industries.