Bio-inspired hydrophobic thin films with nano- and micro-structures find many applications. For this study, the PVA/PEDOT:PSS (PPDOT) composite nanofibers (nanofiber membranes) as the hydrophobic thin film are electrospun. Hydrophobic PPDOT composite nanofibers that are not affected by the electrical properties and viscosity were produced using glutaraldehyde (GA) cross-linkages. Using GA at 2–10% concentration, the surface hydrophobicity of the composite nanofiber allows the removal of dust. GA cross-linking affects the specific surface area of electrospun PPDOT composite nanofibers and carbon–oxygen bonding (C = O) has a significant effect on the surface properties. Bio-inspired nanofiber structures for hydrophobic thin films allow their use for self-cleaning application.