As an effective and environmentally friendly material for corrosion prevention, layered double hydroxide (LDH) films have usually been degraded due to their inherent microporous structure. In this study, graphene derivatives were employed to enhance the corrosion resistance of LDH films. After ultrasonic treatment of a reaction solution mixture containing graphene oxide (GO) powder, a reduced graphene oxide/zinc-aluminum LDH (RGO/Zn-Al LDH) film was in situ synthesized on a magnesium alloy substrate by a one-step facile hydrothermal crystallization process. The characterization results demonstrated that the LDH nanosheets grew on both the GO surface and the magnesium substrate, and thus the agglomeration of graphene was effectively prevented. Furthermore, the GO plates were simultaneously reduced into RGO, which has better corrosion resistance. The as-prepared samples were individually assessed by potentiodynamic polarization measurements, and the RGO/Zn-Al LDH film showed good corrosion resistance with a lower corrosion current density (0.546 μA/cm2) than that of the bare substrate (33.2 μA/cm2) and Zn-Al LDH film (4.33 μA/cm2). The penetration resistance of the Zn-Al LDH film to a corrosive environment was significantly improved through the organic combination with graphene oxide, and this method provides a simple and facile approach to effectively enhance the corrosion protection performance of LDH materials.