Polyaniline, a novel conductive polymer, has been widely used as an anti-corrosive filler. In order to further improve the anti-corrosion performance, polyaniline/graphene (PANI/RGO) composites were prepared by in situ polymerization. And PANI/RGO composite anti-corrosion coatings were also prepared using PANI/RGO as anti-corrosive filler and waterborne polyurethane (WPU) as matrix. The anti-corrosion properties were proven by potentiodynamic polarization curves (Tafel polarization curves), electrochemical impedance spectroscopy and salt spray test analysis of the WPU anti-corrosive coatings. The results showed that the obtained composite coatings reinforced by 0.75 wt% of PANI/RGO composites possessed superior anti-corrosive performance when the graphene content of the filler was 4 wt%.