A systematic study is carried out to determine the optimum electrospinning preparation condition to prepare an adequate electrospun nanofibrous membrane (ENM) for direct contact membrane distillation (DCMD). A structural properties investigation of ENM was carried out because of the significant impact of its architectural structure, nanofiber diameter, inter-fiber space and ENM thickness, on DCMD performance. The morphology, hydrophobicity, mechanical properties, crystallinity and DCMD desalination were investigated. A long-term DCMD experiment (100h) was carried out using 30 g/L NaCl aqueous solution, both in the feed and permeate side of the optimum ENM membrane to evaluate its potential to produce drinkable water in case of lack of distilled water, for instance in a remote area, emergency situation, and/or portable system. In this case, drinkable water could be produced after 28 h with a permeate flux of 57.5 kg/m2.h and a salt rejection factor greater than 99.9%. Another long-term DCMD experiment (65 h) was conducted using 30 g/L NaCl aquesous solution as feed but at a higher temperature and distilled water as permeate to evaluate the desalination stability, wettability and scaling of the optimum ENM. A permeate flux of 58.5 kg/m2.h was obtained with a salt rejection factor greater than 99.9%.