Fabrication of polyvinylidene fluoride (PVDF) hydrophobic asymmetric hollow fiber membranes was studied by introducing inorganic salt LiCl and water soluble polymer polyethylene glycol (PEG) 1500, using N,N-dimethylacetamide (DMAc) as solvent and tap water as the coagulation medium. The membranes properties also were tested and characterized. It is found that the non-solvent additive can increase membranes porosity, ether LiCl or PEG 1500. Because of the addition of PEG 1500, the PVDF membranes obtained a rough topography on the membrane surface and the contact angle of the PVDF membranes increased to 113.50 degrees compared to 89.82 degrees of the PVDF membranes spun without an additive. During direct contact membrane distillation (DCMD) of 0.6 M sodium chloride solution, the PVDF membranes spun with PEG 1500 as a non-solvent additive achieved higher water permeation flux compared to the membranes spun from PVDF/DMAc and PVDF/DMAC/LiCl dopes, but the latter two membranes exhibited higher salt rejection rate.