The self‐assembly of PVPh‐b‐PS in different solvents was studied. Upon replacing toluene by THF as the solvent, the morphology of the resulting aggregates change from core‐shell spheres, rod‐like micelles and vesicles to onion‐like aggregates. With increasing block copolymer concentration, morphologies such as honeycomb‐like films, surfaces of aggregated large porous spheres, or pincushion‐like spheres with protruding tubular vesicle aggregates are observed. These surface‐patterned films show significantly enhanced hydrophobicity. The results suggest that a superhydrophobic behavior can be achieved, with a maximum contact angle of 158°, by using the pincushion‐like micellar structure.