Polystyrene (PS) and polyvinyl chloride (PVC) fibers incorporated into TiO2 nanoparticles and graphene nanoflakes were fabricated by an electrospinning technique, and then the surface morphology and superhydrophobicity of these electrospun nanocomposite fibers were investigated. Results indicated that the water contact angle of the nanocomposite fiber surfaces increases to 178 degrees on the basis of the fiber diameter, material type, nanoscale inclusion, heat treatment, and surface porosity/roughness. This is a result of the formation of the Cassie-Baxter state in the fibers via the nanoparticle decoration, bead formation, and surface energy of the nanofiber surface. Consequently, these superhydrophobic nanocomposite fibers can be utilized in designing photoelectrodes of dye-sensitized solar cells (DSSCs) as self-cleaning and anti-icing materials for the long-term efficiency of the cells.