© 2017 by the authors.Electrospun membranes are gaining interest for use in membrane distillation (MD) dueto their high porosity and interconnected pore structure however, they are still susceptible towetting during MD operation because of their relatively low liquid entry pressure (LEP). In thisstudy, post-treatment had been applied to improve the LEP, as well as its permeation and saltrejection efficiency. The post-treatment included two continuous procedures: heat-pressing andannealing. In this study, annealing was applied on the membranes that had been heat-pressed.It was found that annealing improved the MD performance as the average flux reached 35 L/m2hor LMH (>10% improvement of the ones without annealing) while still maintaining 99.99% saltrejection. Further tests on LEP, contact angle, and pore size distribution explain the improvementdue to annealing well. Fourier transform infrared spectroscopy and X-ray diffraction analysesof the membranes showed that there was an increase in the crystallinity of the polyvinylidenefluoride-co-hexafluoropropylene (PVDF-HFP) membrane also, peaks indicating the α phase ofpolyvinylidene fluoride (PVDF) became noticeable after annealing, indicating some βand amorphousstates of polymer were converted into the α phase. The changes were favorable for membranedistillation as the non-polar α phase of PVDF reduces the dipolar attraction force between themembrane and water molecules, and the increase in crystallinity would result in higher thermalstability. The present results indicate the positive effect of the heat-press followed by an annealingpost-treatment on the membrane characteristics and MD performance.