GaAs wafers have been decorated with Ag nanoplates through direct galvanic reaction between aqueous AgNO₃ solutions and GaAs, resulting in Ag nanoplate/GaAs composite surfaces with varying hydrophobocity after the Ag nanoplates were coated with self-assembled monolayers of alkyl thiol molecules. By carefully controlling the reaction conditions, such as growth time and concentration of the AgNO₃ solution, the size, thickness, and surface roughness of the individual Ag nanoplates can be tuned in order to produce different topographic structures and roughness of the composite surfaces, which in turn influences the hydrophobicity of the surfaces. The as-synthesized composite surfaces have been found to exhibit various levels of hydrophobicity and different wetting states such as the Wenzel wetting state, Cassie impregnating wetting state, and Cassie nonwetting state. The relationship between surface structure and hydrophobic state is also discussed.