This paper presents a new method for the patterning of self-assembled monolayers (SAMs) using UV light. Azidoformate-terminated SAMs starting from 18-acetoxy-octadecyltrichlorosilane SAMs on silicon, prepared for the first time, are electrophilic and photosensitive, and can be patterned by UV irradiation through a mask. The resulting structured surfaces are still electrophilic and can be reacted with nucleophilic functions, for example, primary amines.