Most commercial polymeric membranes are prepared by phase inversion. The performance of the membranes depends greatly on the morphology of the porous structure formed during the different steps of this process. Researchers in this field have found it extremely difficult to foresee how a change in the composition of the polymer solution will affect pore formation without a set of methods designed to yield detailed knowledge of the morphological structure. This paper reports the new potential associated with X-ray synchrotron microtomography to characterize the 3D structure of a PvDF hollow fibre microfiltration membrane prepared by phase inversion. 3D morphological data obtained from the ID 19 line at the ESRF are presented. The membrane actually appears as a complex three-dimensional bi-continuum of interconnected pores. Within the hollow fibre structure, different regions with various thicknesses and pore size distributions have been identified and well characterized. Transversal views show the amsotropic finger-like structure of pores, while longitudinal sections reveal a honeycomb structure which resembles the structure of highly concentrated water in oil emulsion or dispersion. This typical structure might be obtained during the phase inversion process. How the phase inversion process may result in these morphologies is finally discussed. (c) 2007 Elsevier B.V. All rights reserved.