In this paper, we tried to fabricate a compact and thick mercapto functional silica sol-gel coating to achieve excellent corrosion resistance performance on copper.A detailed comparative study of alkylthiol self-assembled monolayers (SAMs) and mercapto functional silica sol-gel coating prepared by 1-octanethiol (OT), n-dodecanethiol (DT) and (3-mercaptopropyl)trimethoxysilane (MDTMS) was carried out.The elements composition and chemical bonding of the protective coatings were characterized by X-ray photoelectron spectroscopy (XDS) and flourier transform infrared spectroscopy (FTID).In addition, the micro/nano-structure morphologies of as-prepared coatings on copper surface were investigated by atomic force microscope (AFM).The wettability of various coatings was investigated by contact angle measurement instrument.Finally, the anti-corrosion ability of the coatings was characterized using an electrochemical workstation.Desults demonstrated that compared to other alkylthiol SAMs, the Cu-MDTMS sol-gel coating showed the best anti-corrosion property in sodium chloride solution because it owned a multiple hierarchic Si-0-Si network structure, thus to achieve a higher range of thickness, lengthen the diffusion path way of corrosive medium.It was also found that compact and thick mercapto functional silica sol-gel coating showsbetter corrosion resistance performance than other SAMs of the same type.