High-performance polybenzimidazole (PBI) hollow-fiber membranes (HFMs) were fabricated through a continuous dry-jet wet spinning process at SRI International. By adjusting the spinning air gap from 4″ (10.2 cm) to 0.5″ (1.3 cm), the HFM pore sizes were enlarged dramatically without any significant change of the fiber dimensional size and barrier layer thickness. When fabricated with an air gap of 2.5″ (6.4 cm) and a surface modified by NaClO solution, the PBI HFM performance was comparable to that of a commercial reverse osmosis (RO) HFM product from Toyobo in terms of salt (NaCl) rejection and water permeability. The PBI RO HFM was positively surface charged in acidic conditions (pH < 7), which enhanced salt rejection via the Donnan effect. With an air gap of 1.5″ (3.8 cm), the PBI HFM rejected MgSO₄ and Na₂SO₄ above 95%, a result that compares favorably with that achieved by nanofiltration. In addition, the PBI HFM has a defect-free structure with an ultra-thin barrier layer and porous sublayer. We believe PBI HFMs are ideal for water purification and can be readily commercialized.