The self-assembled films of methyloctyldimethoxysilane (MODMS) and fluorooctylmethyldimethoxysilane (FODMS) were prepared on silicon surfaces and evaluated with AFM, water contact angle measurement, and X-ray photoelectron spectroscopy. Superhydrophobic surfaces were obtained by cooperation of MODMS and FODMS self-assembly with surface roughening. The results showed that preparing closely packed self-assembled films and fabricating surface nanometer-scale and micrometer-scale binary roughness can achieve superhydrophobic films with a water contact angle larger than 156degrees. The difference between solution deposition and chemical vapor deposition is also investigated. Moreover, superhydrophobic surfaces created with MODMS and FODMS show the different water-adhesion effects, which could have great significance on liquid microtransport in microfluid devices.