In this paper, polyimide (PI) nanofibers with diameters of 300-400 nm are successfully produced via electrospinning methods. Electrospinning parameters such as polymer concentration, applied voltage, feed rate, and the needle-to-collector distance have been studied systematically to investigate their effects on morphology. The smooth-surfaced uniform nanofibers with diameters ranging from 300 to 400 nm can be obtained at the optimal parameters, further discussed herein. The synthesized PI nanofibers show improved thermal stability and a high hydrophobicity with a maximum contact angle of 140.7 degrees and low surface energy of 3.12 mN.m(-3), indicating potential applications as self-cleaning materials, such as solar panel cleaning, window glass cleaning, and cements.