In this paper, we propose a enhanced anti-corrosion property of the ground system by coating the CNT/PVDF composite film on it. Polymer material used for preventing the corrosion of ground system is polyvinylidene fluoride (PVDF), and conducting filler for obtaining conductivity of the composite film is multi-walled carbon nanotubes (MWCNTs). The MWCNTs were dispersed in the organic solvent of methyl ethyl ketone 2-butanone (MEK) with different concentration ratios, and the PVDF was solved in the MEK solvent with constant concentration ratio of 1 wt%. The CNT/PVDF composite solution was perpared by mixing and re-dispersing the CNT solution and the PVDF solution. Finally, the CNT/PVDF composite films were fabricated by the spray coating method using the above composite solution. Electrical conductivity, surface states, and anti-corrosion property of the CNT/PVDF composite films coated on the Cu substrate were evaluated. We found that the CNT/PVDF composite film showed relatively low resistance, hydrophobic surface state, and chemical stability. Consequently, we could improve the anti-corrosion property and maintain the electrical conductivity of the ground system by coating the CNT/PVDF composite film on it.