Membrane distillation is a growing technology that can address the growing problem of water shortage. The implementation of renewable energy and a reduction in the environmental impact of membrane production could improve the sustainability of this process. With this perspective, porous hydrophobic polyvinylidene fluoride (PVDF) membranes were prepared using triethyl phosphate (TEP) as a green solvent, using the non-solvent induced phase separation technique. Different amounts of carbon black were added to dope solutions to improve the photothermal properties of the membranes and to enable direct heating by solar energy. By optimizing the preparation conditions, membranes with porosity values as high as 87% were manufactured. Vacuum membrane distillation tests carried out using a concentrated NaCl solution at 50 °C showed distillate fluxes of up to 36 L/m2 h and a complete salt rejection. Some preliminary studies on the photothermal performance were also conducted and highlighted the possibility of using such membranes in a direct solar membrane distillation configuration.