Superhydrophobic surfaces with high water contact angles and low slide angles have drawn worldwide attention for their excellent water resistance, anti-contamination, and self-cleaning property. Herein, hydrophobic coatings were facilely fabricated on porous glass fiber nonwoven mats through immersing the substrates in a highly fluorinated emulsion, which was prepared with cross-linkable sulfonyl macro emulsifiers. The superhydrophobic properties and the long term stability of porous glass fiber mats were optimized by incorporating the synthesized emulsion and cross-linking agents, Melcross 03, together into the coating process. Notably, the superhydrophobicity of modified glass fibers can be ascribed to the surface enrichment of fluorine and lack of migration from reacted polar sulfonyl groups. As a result, the largest water contact angle of the coated glass fiber obtained is 151.4° and the smallest slide angle measured is only 3.9°, exhibiting superior water repellency to other fluorinated emulsion coatings. Moreover, the great anti-fouling properties and water/oil separation performance suggest that the facile method is promising for varied applications.