Using the prepared La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) hollow fibre membranes via the phase inversion and sintering technique, the catalytic perovskite hollow fibre membrane reactors (HFMRs) without or with additional OCM catalyst inside the fibre lumen were designed and tested for the methane oxidative coupling reaction. LSCF powder possesses almost zero C-2 selectivity, but the blank LSCF hollow fibre membrane reactor shows a higher C-2 selectivity up to 71.9%. Application of additional SrTi0.9Li0.1O3 catalyst in the fibre lumen is able to increase methane conversion and oxygen permeation rate remarkably but decrease the C-2 selectivity. There is an optimum temperature to obtain the maximum C-2 selectivity for either the packed or the blank membrane reactor. The membrane reactor exhibits appreciable advantages over the traditional packed bed reactor. A maximum C-2 yield close to 21% can be achieved in the packed hollow fibre membrane reactor. (c) 2007 Elsevier B.V. All rights reserved.