A biopolymer coating on copper was prepared based on chitosan nanocomposite and its corrosion inhibition efficiency was investigated. Inclusion of silica nanoparticles substantially reduces swelling ratio of chitosan coating while enhancing its thermal stability. The corrosion resistance of chitosan-based coatings is improved by introducing 2-mercaptobenzothiazole and silica in the matrix. It is found that upon crosslinking the chitosan coatings, a higher corrosion resistance could be achieved and the highest inhibition efficiency for chitosan nanocomposite coatings is calculated as 85%. The corrosion mechanism is found closely related to mass transition and diffusion process, and also the polarization resistance contributes to the impedance. Calculated impedance using Kramers-Kronig transformation shows good agreement with experimental values, thus validating the impedance measurements. This study exhibits the enhanced efficiency of nanocomposite and potential of chitosan coatings in corrosion prevention for copper.