In this study, syndiotactic 1,2-polybutadiene (s-PB)/azobisisobutyronitrile (AIBN) membranes were prepared via electrospinning. The obtained membranes were intensively investigated by contact angle analyzer, differential scanning calorimetry (DSC) and environmental scanning electron microscope (ESEM). With increasing the concentration of spinning solution, the obtained membranes were changed from hydrophobic to surperhydrophobic and the contact angle (CA) as high as 157 at higher s-PB concentration. In addition, the s-PB/AIBN membrane cross-linked completely through heat treatment and superhydrophobic property of s-PB/AIBN membrane has not changed. The diameter of cross-linked fiber-based membrane was much thinner than that of the uncross-linked fibers.