In recent years, superhydrophobic surfaces have attracted significant attention due to their promising applications, especially in ice prevention, reduction in air resistance, and self-cleaning. This study utilizes femtosecond laser processing technology to prepare different surface microstructures on polytetrafluoroethylene (PTFE) surfaces. Through experiments, it investigates the relationship between the solid–liquid contact ratio and surface hydrophobicity. The shape of water droplets on different microstructure surfaces is simulated using ANSYS, and the relationship between surface microstructures and hydrophobicity is explored in the theoretical model. A superhydrophobic surface with a contact angle of up to 166° was obtained by machining grooves with different spacings in polytetrafluoroethylene sheets with femtosecond laser technology. Due to the micro- and nanostructures on the surface, the oleophobicity of the processed oleophilic PTFE surface is enhanced.