By using mercaptopropyltrimethoxysilane (MPTS) self-assembled monolayers (SAMs), electroless silver plating is developed for the metallization of near-field optical fiber probes. This method has the advantages of controllability, no pinholes, convenience, low cost, and smooth tip surface. The metallized probes are characterized by optical microscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDXS).