Interest in using graphene and graphene oxide (GO)-based polymer composites as effective corrosion inhibitors is mounting due to their fascinating characteristics such as large surface area coverage, good adhesion property, chemical resistivity, hydrophobicity, chemical and mechanical stability, and so on. The major works based on anticorrosive performances of polymeric composites containing graphene and GO are the focus of this chapter. The key objective of this chapter is to outline recently developed and explored polymeric composites of graphene and GO, the detailed explanation of the corrosion inhibition mechanism, and their use as effective anti-corrosive coating for protecting mild steels exposed to various corrosive electrolytic solutions.