A series of novel thiazoles incorporated with hydrocarbon and fluorocarbon chains using to form self-assembled monolayers (SAMs) on copper substrates were prepared. The SAMs were investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and contact angle measurements, and the results support that these thiazoles are successfully adsorbed on the substrates, forming hydrophobic films. The anti-corrosion effect of the SAMs was determined by weight loss experiments, scanning electron microscopy and electrochemical methods. It is revealed that the protection ability of the SAMs is detected by the thiazoles concentration, immersion time and fluorocarbon chain length. Quantum chemical calculations were employed to correlate the adsorption mechanism with the structure of the thiazoles molecules.