Unique hierarchical pore structures were fabricated by simply irradiating an electron beam onto silicone grease films. The hierarchical pore structures consisted of micrometer- sized pores and macroporous walls. Due to the high surface roughness, the hierarchical pore structures exhibited both superhydrophobicity with a water contact angle (CA) of 170 degrees and superhydrophilicity with an extremely low water CA of 3 degrees after the chemical treatment of the surfaces. In addition to the hierarchical pore structures, sponge-like pore structures were also fabricated by the electron irradiation of silicone grease films.