A systematic study of the air gap effects on both the internal and the external morphology, permeability and separation performance of polyvinylidene fluoride (PVDF) hollow fiber membranes has been carried out. The hollow fibers were prepared using the dry-jet wet spinning process using a dope solution containing PVDF/ethylene glycol/N, N-dimethylacetamide with a weight ratio of 23/4/73. Ethanol aqueous solution, 50% by volume, was used as internal and external coagulants. The inner and the outer surfaces of the prepared hollow fibers were analyzed by atomic force microscopy (AFM), while their cross-sectional structure was studied by scanning electron microscopy (SEM). Ultrafiltration experiments were conducted using non-ionic solutes of different molecular weights. The results show that both the pore sizes and nodule sizes have a log-normal distribution. The pore size, nodule size and roughness parameters of the inner and outer surfaces of the hollow fibers were affected by the air gap distance. Alignment of nodules to the spinning direction was observed. Experimental results indicate that an increase in air gap distance, from I to 80 cm, results in a hollow fiber with a lower permeation flux and a higher solute separation performance due to the decrease of the pore size. AFM analysis reveals that the air gap introduces an elongational stress because of gravity on the internal or external surfaces of the PVDF hollow fibers. At low air gap distance, the inner surface controls the ultrafiltration performance of the PVDF hollow fiber membranes because of its lower pore size, while at high air gap lengths the inner pore size becomes larger than the outer pore size. The turning point was observed at an air gap distance of 20.3 cm. (C) 2003 Elsevier Ltd. All rights reserved.