Summary: A highly hydrophobic surface with a water contact angle of 148.0° has been constructed by depositing salicylic acid‐doped polyaniline (PANI‐SA) spheres on a glass substrate using a template‐free method. The hydrophobicity originates from the contribution of the air trapped in the inter‐space of a rough surface aggregated by micro‐ and nanospheres. Moreover, the deposition time strongly affects the hydrophobicity of the PANI‐SA spheres deposited on the substrate. The formation mechanism and hydrophobic origin of the PANI‐SA spheres deposited on the substrate are discussed.