Asymmetric ceramic hollow fibre membranes and membrane supports have been prepared using a combined phase inversion and sintering technique for use in a multifunctional catalytic membrane reactor. The asymmetric structure is such that the fibre may simultaneously function either as a porous membrane and a matrix for catalyst deposition, or as a porous support for the coating of a gas separation layer and a matrix for catalyst deposition. The effectiveness of catalyst deposition depends strongly on the pore size distribution of the membrane or membrane support, which is bimodal in nature and is affected by the calcination temperature and the fibre preparation parameters. The effect of the calcination temperature and preparation parameters on the pore size distribution and fibre morphology have been studied systematically with regard to catalyst deposition and fibre mechanical strength and a route to optimizing the fibre structure has been suggested. (C) 2010 Elsevier B.V. All rights reserved.