The development of permanent superhydrophobic surfaces has attracted significant attention due to their usage in many applications, particularly in environmental and biomedical remediations. Among the various fabrication techniques, electrospinning has emerged as an advantageous and flexible method for fabricating nanofibers with tailored surface characteristics. In this study, we explore the enhancement of superhydrophobic properties of nanofibers by incorporating Teflon particles into matrices of polystyrene (PS) and polyvinyl chloride (PVC) through the electrospinning process. Electrospinning was employed to fabricate three-dimensional (3D) structured nanofibers with and without highly hydrophobic Teflon particles with an average particle size of 180 nm. Following the fabrication of these nanofibers, a series of heat treatments were applied at various temperatures (0°C, 50°C, 75°C, 100°C, and 125°C) for different durations (30 min, 1 h, 2 h, and 4 h) to improve the surface properties of the nanofibers further. The hydrophobicity of the nanofibers was assessed through water contact angle (WCA) measurements, which confirmed that all nanofibers exhibited hydrophobic behavior. The addition of Teflon particles, combined with heat treatment, significantly enhanced the hydrophobicity of the nanofibers, resulting in WCA values of 155.75° for PS nanofibers and 151.62° for PVC nanofibers, thereby categorizing them as having permanent superhydrophobic properties. Further characterization of the nanofibers was conducted using scanning electron microscopy (SEM) and Fourier-transform infrared (FTIR) spectroscopy to analyze their surface morphology and chemical compositions. These analyses indicated that the nanofibers consistently fell within the submicron to nanoscale range, with a uniform distribution of Teflon particles observed across the nanofiber surfaces. The resultant PS nanofibers exhibited fiber diameters in the range of 400 nm to 1 μm, while the PVC nanofibers ranged from 200 to 600 nm. Collectively, these results suggest that fabricated 3D nanofibers are viable candidates for a range of environmental and health remediations and energy mitigations. © 2025 Wiley Periodicals LLC.