Anisotropic dewetting polydimethylsiloxane (PDMS) surfaces, which consist of groove-like micro/nanostructures (so-called hierarchical structures), are fabricated using an ultrashort pulsed laser. The contact angles (CAs) are measured parallel to the microgrooves, which are always larger than those measured perpendicular to the microgrooves, exhibiting a superhydrophobic anisotropy of approximately 4° on these fabricated PDMS surfaces at optimized parameters. These pulsed-laser irradiated surfaces exhibit enhanced hydrophobicity with CAs that increase from 116° to 156° while preserving the anisotropic dewetting. Additionally, the wettability of the surfaces with different morphologies is investigated. The temporal evolution of the wettability of the pulsed-laser irradiated PDMS surface is also observed within the first few hours after pulsed laser irradiation.