A series of microporous PVDF membranes were prepared by isothermal immersion-precipitation of PVDF/TEP casting dopes in both soft and harsh coagulation baths. Morphologies of the membranes’ top surfaces were found to depend strongly on the bath strength, which could be controlled by the TEP content in the bath. By changing the bath gradually from pure water to 70% TEP, the top surface evolved from a dense skin-like (asymmetric) to a totally open porous morphology (symmetric). The latter structure could similarly be obtained by precipitation of the same dope in an alcoholic bath, e.g., 1-butanol. Membrane distillation processes to desalt sodium chloride aqueous solutions were conducted using various prepared membranes and two commercial microporous membranes, PTFE (Toyo, Japan, code: J020A330R) and PVDF (GE, USA, code: YMJWSP3001). The permeation fluxes were compared and correlated with the morphologies of the tested membranes.