The development of sustainable, cost-effective, efficient water collection materials and methods for continuous freshwater production is crucial for many regions especially in arid and semiarid regions of the world. The world population growth, urbanization, depleting water resources, and global climate change have intensified this crisis. The concern is drastically increasing and therefore scientists and engineers are challenged with urgently developing viable solutions for this problem. Also, the production of different plastic wastes is increasing day-by-day, and therefore, a growing concern to the serious environmental challenges. These wastes are rarely dissolved by microorganisms, and hence, the recycling of these plastic wastes into value-added materials could be a sustainable solution to addressing environmental issues. In this work, recycled expanded polystyrene (REPS) foam with various proportions of titanium dioxide (TiO2) nanoparticles and aluminum (Al) microparticles were spun into superhydrophobic nanocomposite fibers using electrospinning technique and used for harvesting fog from the atmosphere. The fiber morphology, surface hydrophobicity, and fog harvesting capacity of the nanocomposite fibers were investigated. Test results reveal that the as-prepared nanocomposite fibers exhibit superhydrophobic characteristics with a water contact angle of 152.03° and an efficient fog harvesting capacity of 561 mg/cm2 /hr. The nanotechnology-based collection systems are unique because of the fine structures of the nanomembranes. Thus, the electrospun superhydrophobic nanocomposite fibers from REPS have various industrial applications including water collection, water filtration, tissue engineering, and composites, etc and the produced water can be used for drinking, agriculture, industrial, and other purposes.