Three-dimensional nano-architectures with varying shape, morphology and size were fabricated by the phase separation of methyltrichlorosilane (CH(3)SiCl(3)) on commercially available glass and SiO(2) substrates. By changing the synthesis conditions, CH(3)SiCl(3) nanostructures evolved from discrete to quasi-network or from fibrous to spherical forms. Individual nanofibers and nanospheres have diameters of 18-90 and 240-300 nm, respectively, while the film thicknesses could reach 320 nm. The possible mechanisms for the three-dimensional growth of nanofibers and nanospheres are proposed. The resultant morphologies exhibited two main energy states: Wenzel and Cassie-Baxter states. Moreover, superhydrophobic surfaces with both high contact angle and high hysteresis resulted from the growth of the nanostructures. The new approaches presented herein are important additions to the current range of surface modification methods and could harness novel physical and chemical properties conducive to optimal performance in biosensing, antistiction, droplet manipulation, drag reduction, protein adsorption, and cell adhesion studies.