This work reports the coaxial elcctrospinning of poly(vinylidene fluoride) (PVDF) Teflon amorphous fluoropolymer (AF) and Teflon AF-PVDF core-sheath nanofiber mats yielding superhydrophobic properties. The coaxial electrospinning configuration allows for the electrospinning of Teflon AF, a nonelectrospinnable polymer, with the help of an electrospinnable PVDF polymer. PVDF-Teflon AF and Teflon AF-PVDF core sheath fibers have been found to a have mean fiber diameter ranging from 400 nm to less than 100 nm. TEM micrographs exhibit a typical core sheath fiber structure for these fibers, where the sheath fiber coats the core fiber almost thoroughly. Water contact angle measurements by sessile drop method on these core sheath nanofiber mats exhibited superhydrophobic characteristics with contact angles close to or higher than 150 degrees. Surprisingly, PVDF-Teflon AF and Teflon AF-PVDF nanofiber mat surface properties were dominated by the fiber dimensions and less influencd by the type of sheath polymer. This suggests that highly fluorinated polymer Teflon AF does not advance the hydrophobicity beyond what surface physics and slightly fluorinated polymer PVDF can achieve. It is concluded that PVDF-Teflon AF and Teflon AF-PVDF core-sheath clectrospun nanofiber mats may be used in lithium (Li)-air batteries.