Graphene oxide (GO), derived from the two-dimensional nanosheet graphene, has received unprecedented attention in the field of metal corrosion protection owing to its excellent barrier performance and various active functional groups. In this review, the protection mechanism “labyrinth effect” of composite coatings against metal corrosion was demonstrated systematically. The origination, structure and properties of GO were also analyzed. Their poor dispersion in polymer and tendency to aggregate as nanofillers in composite coatings are the main limitations during application of the coating fillers. In addition, a comprehensive overview on the perspectives of the surface modification of GO and the multi-functionalization of the composite coatings based on GO were given in particular. Green modification methods, reasonable arrangement of GO sheets in composites and development of multi-functional coatings remain challenges in current studies and should be a focus in the future development of GO-based anticorrosive coatings. This review is of value to researchers interested in the design and application of GO in corrosion protection coatings.