Silicon surfaces are promising interfaces because they are mechanically and chemically resilient, able to resist wear in aqueous and organic environments, and display good electrical properties. There are a number of methods that are used to thiolate a silicon surface, notably through the attachment of molecules that contain terminal-SH moieties. These methods usually suffer from long reaction times. In the present work, we developed an alternative method for thiolation of a silicon surface by introducing terminal thiol groups directly onto the silicon surface. The developed wet chemical process relies on chlorination and then surface thiolation and requires less time for grafting thiol groups on the silicon substrate. X-ray photoelectron spectroscopy (XPS) and contact angle measurement were employed for surface characterization after each step.