This work evaluates the operational stability of six different supported liquid membranes (SLMs) based on ionic liquids (ILs). [bmim(+)][PF6-], [bmim(+)][BF4-] and [bmim(+)][NTf2-] were used as supporting phase in Nylon (R) and Mitex (R) membranes. Scanning electron microscopy (SEM) combined with energy dispersive X-ray (EDX) analysis was used to characterize the membrane surface morphologically and examine the global chemical composition of the membranes and the distribution of the ILs within them. Study of the freshly impregnated membranes showed that, in all cases, the ILs were homogeneously distributed, mostly filling the pores of the membranes although, in some cases, a small amount of excess of IL was located on the external membrane surface. Stability tests were performed by keeping the respective impregnated membranes immersed for a week in a diffusion cell including two independent compartments and using n-hexane/n-hexane as the respective feed and receiving phases. The SEM-EDX study of membranes after continuous operation showed that the ILs were still retained within the membrane pores and only small losses of the IL initially located on the external surface were observed. These observations are in complete agreement with the ionic losses determined by mass balance. (C) 2007 Elsevier B.V. All rights reserved.