The development of surface engineering techniques to tune-up the composition, structure, and function of materials surfaces is a permanent challenge for the scientific community. In this chapter, the electrospinning process is proposed as a versatile technique for the development of highly hydrophobic or even superhydrophobic surfaces. Electrospinning makes possible the fabrication of nanostructured ultrathin fibers, denoted as electrospun nanofibers (ENFs), from a wide range of polymeric materials that can be deposited on any type of surface with arbitrary geometry. In addition, by tuning the deposition parameters (mostly applied voltage, flow rate, and distance between collector/needle) in combination with the chemical structure of the polymeric precursor (functional groups with hydrophobic behavior) and its resultant viscosity, it is possible to obtain nanofibers with highly porous surface. As a result, functionalized surfaces with water-repellent behavior can be implemented in a wide variety of industrial applications such as in corrosion resistance, high efficient water-oil separation, surgical meshes in biomedical applications, or even in energy systems for long-term efficiency of dye-sensitized solar cells, among others.