Superhydrophobicity of a substrate is the result of a low surface energy and proper surface roughness. In the present research, the potential roughening effect of using nano-TiO2 (NT) in a PET electro-spinning solution followed by an alkaline modification of the synthesized bats was investigated to create appropriate surface roughness while a low surface energy was achieved in owing to a layer of fluorocarbon coating. The results were evaluated via employing FTIR, SEM, digital microscopy, 3 M water repellency, water contact angle, and sliding angle. The best result of hydrophobicity was achieved by the alkaline modified-fluorocarbon coated NT (5.5%)/PET fibrous bat with the 3 M water repellency of 10, contact angle of more than 150° (155.9 ± 0.1°), and sliding angle of less than 10° (6.1 ± 1.9°) due to a multiscale surface roughness obtained by the fibrous bat structure itself, and roughening effect of the NT as well as alkaline solution surface etching.