Membrane distillation (MD) is an attractive thermally-driven membrane process for desalination, brine and wastewater treatment. One of the main obstacles impeding MD application is the absence of effective MD membranes with sufficient water permeability and long-term stability. Attributed to the outstanding hydro-phobicity, excellent thermal and chemical resistance, the most ideal polymer to develop MD membrane is polytetrafluoroethylene (PTFE). However, the fabrication of PTFE membranes is challenging due to its poor processability. This work describes a novel strategy to develop superhydrophobic and highly porous PTFE membranes via electrospinning. The hydrophobic nanoparticles 8 vinyl-grafted polyhedral oligosilicone (vinyl-POSS) were firstly incorporated into PTFE nanofibers to promote the crystallization of PTFE nanofiber, enhance nanofiber roughness, and improve membrane mechanical robustness and porosity. The effects of vinyl-POSS concentration, temperature and salt concentration of feed solutions on MD performance of PTFE/POSS nanofibrous membranes were investigated systemically in this study. The optimized PTFE/POSS nanofibrous membrane #POSS-2 has a three-dimensional (3D) superhydrophobic property with a water contact angle of 151 +/- 4 degrees. It exhibited a competitive water flux of 40 +/- 2 Lm(-2) PH-1 in the direct contact membrane distillation (DCMD) process when the feed and permeate temperatures were 60 and 20 degrees C, respectively. Moreover, #POSS-2 possessed an excellent long-term stability in a 200-h continuous DCMD operation.