In this study, a novel hydrophobic, microporous membrane was fabricated from styrene-butadiene-styrene (SBS) polymer using electrospinning and evaluated for membrane distillation applications. Compared to a commercially available polytetrafluoroethylene (PTFE) membrane, the SBS membrane had larger membrane pore size and fiber diameter and comparable membrane porosity. The fabricated SBS showed slightly lower water flux than the PTFE membrane because it was two times thicker. However, the SBS membrane had better salt rejection and most importantly could be fabricated via a simple process. The SBS membrane was also more hydrophobic than the reference PTFE membrane. In particular, as temperature of the reference water liquid increased to 60 °C, the SBS membrane remained hydrophobic with a contact angle of 100° whereas the PTFE became hydrop hilic with a contact angle of less than 90°. The hydrophobic membrane surface prevented the intrusion of liquid into the membrane pores, thus improving the salt rejection of the SBS membrane. In addition, the SBS membrane had superior mechanical strength over the PTFE membrane. Using the SBS membrane, stable water flux was achieved throughout an extended MD operation period of 120 h to produce excellent quality distillate (over 99.7% salt rejection) from seawater.