The production of various plastic wastes is increasing day by day and has become a growing concern to the serious environmental challenges. This type of waste is rarely resolved by microorganisms; hence, the recycling to the value-added materials is essential. In recent years, superhydrophobic surfaces have gained increasing attention in both fundamental research and practical applications due to multi-functionalities. Recycling the polymer wastes for the fabrication of superhydrophobic nanofibers could be a partial solution to environmental issues. The superhydrophobic surfaces can be fabricated by controlling the chemical composition and topological structure using various methods. In this work, recycled expanded polystyrene (EPS) foam with various proportions of titanium dioxide nanoparticles (TiO2 NPs) and aluminum microparticles (Al µPs) was spun into superhydrophobic nanocomposite fibers using the facile electrospinning technique. The morphology, surface hydrophobicity, and thermal properties of the nanocomposite fibers were investigated. Test results showed that the as-prepared nanocomposite fibers exhibit superhydrophobic characteristics with a water contact angle of 152°. Also, the effect of heat treatment on the surface hydrophobicity of the nanocomposite fibers was analyzed. The electrospun superhydrophobic nanocomposite fibers from recycled EPS foam have various industrial applications, including water collection, water filtration, tissue engineering, and composites.