Mercaptopropyltrimethoxysilane (MPTS) was used to form self-assembly monolayers (SAMs) on glass slides, which was verified by using X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES). Electroless plating of Ag was performed on the SAMs-modified glass slide. XPS study showed that Ag colloids formed in solution were successfully and hard anchored on SAMs through chemical bonds. Scanning electron microscopy (SEM) analysis illustrated that Ag film on the SAMs-modified glass showed more predominant in durability of temperature than that on conventionally modified glass.