Superhydrophobic and superhydrophilic properties of chemically-modified graphene have been achieved in larger-area vertically aligned few-layer graphene nanosheets (FLGs), prepared on Si (111) substrate by microwave plasma chemical vapor deposition (MPCVD). Furthermore, in order to enhance wettability, silicon wafers with microstructures were fabricated, on which graphene nanosheets were grown and modified by a chemical method to form hydrophilic and hydrophobic structures. A superhydrophilic graphene surface (contact angle 0°) and a superhydrophobic graphene surface (contact angle 152.0°) were obtained. The results indicate that the microstructured silicon enhances the hydrophilic and hydrophobic wettabilities significantly.