Trichlorosilanes nanostructures have been fabricated on glass substrates through a fast and facile liquid phase method and the impact of alkyl length on surface nanostructures and the corresponding wettability have been studied. With the increase of alkyl chain length, the prepared surfaces showed different surface geometries on shape, size and quantity, as well as the corresponding wettability. The competition between the decrease of the reactivity caused by the raise of the steric effect and the increase of the alkyl hydrophobicity with the variation of alkyl length is considered to be responsible for these behaviors.