In this project, an unsupported electrospun poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) membrane was used for water desalination using direct contact membrane distillation (DCMD). The membrane was electrospun using a laboratory-scale machine with multiple nozzles that was developed in-house. Critical process parameters, including the applied voltage and polymer concentration, were optimized to obtain bead-free electrospun membranes with fiber diameters less than 300 nm. To improve the membrane thermal stability and performance, the selected electrospun membrane was heat-pressed at 160°C. The untreated and heat-pressed membranes were tested in a DCMD setup at different feed temperatures (60, 70, and 80°C) and feed flow rates (0.4, 0.6, and 0.8 L/min), while maintaining the permeate temperature and flow rate at 20°C and 0.2 L/min, respectively. The modified electrospun membrane exhibited a very high permeate flux (>37.5 kg/m2/h) and a salt rejection rate of 99.99% at a feed temperature of 70°C. The performance of the heat-pressed unsupported PVDF-HFP electrospun membrane was nearly identical to a commercially available polytetrafluoroethylene (PTFE) supported membrane. These promising results demonstrate that relatively low-cost electrospun membranes can be easily produced and successfully used in DCMD to minimize the capital cost and increase the energy efficiency of the process.