Porous polyvinylidene fluoride (PVDF) hollow-fiber membranes with high porosity were fabricated using the immersion precipitation method. Dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP) were used as solvent, respectively. In addition, polyvinylpyrrolidone (PVP), lithium chloride, and organic acids were employed as nonsolvent additives. The effects of the internal and external coagulation mediums on the resulting membrane properties were also investigated. The resulting hollow-fiber membranes were characterized in terms of maximum pore radius, mean pore radius, effective surface porosity as well as wetting pressure. The structures of the prepared hollow fibers were examined using a scanning electron microscope.