Layered double hydroxides (LDHs) exhibit anion exchange properties and adjustable characteristics, which make them suitable for applications in the field of anticorrosion. However, the smooth growth pattern of a single LDHs nanosheet limits its effectiveness in blocking corrosive media. Graphene oxide (GO) has a large specific surface area and numerous oxygen-containing functional groups on its surface, which can form strong interactions with polar molecules. This inhibits the migration of small ions, such as Cl − . In this work, Ce was incorporated into a micro-arc oxidation (MAO) coating on the AZ31 alloy by immersion in a cerium salt solution, and GO was incorporated using a hydrothermal solution to prepare layered double hydroxide composite coating (Ce/LDHs-G). The significance of charge transfer resistance ( R ct ) mainly reflects the charge transfer process at the electrode/electrolyte interface. The R ct of Ce/LDHs-G increased by one order of magnitude compared to MAO coating. The corrosion current density ( i corr ) of Ce/LDHs-G coating was 3.73 × 10 −8 A cm −2 , lower than that of MAO coating (1.56 × 10 −6 A cm −2 ). Additionally, the cumulative hydrogen evolution over 336 h was lower, indicating that Ce/LDHs-G coating provides effective corrosion protection for the AZ31 alloy.