A novel way of producing superhydrophobic surfaces by applying a self-assembled monolayer (SAM) to silicon micro/nano-textured surfaces is presented in this paper. The micro/nano-textured surfaces on silicon substrates were generated by the aluminum-induced crystallization (AIC) of amorphous silicon (a-Si) technique. Octadecyltrichlorosilane (OTS) SAMs were then applied to the textured surfaces by dip coating. The topography and wetting properties of the resulting surfaces were characterized using scanning electron microscopy (SEM) and a video-based contact angle measurement system. The results show that by introducing OTS SAMs on the silicon micro/nano-textured surfaces, superhydrophobic surfaces with water contact angles (WCAs) of 155° were obtained, as compared to the WCAs of OTS-modified smooth silicon surfaces of about 112°. Surface topography was found to directly influence the WCA as predicted by the Cassie-Baxter model.