The membrane process concept coupled with phase inversion technique has been successfully applied for the first time for the preparation of ionic liquid (IL) encapsulated microspheres using polyetheretherketone with card group (PEEKWC), trihexyl(tetradecyl)phosphonium chloride[CYPHOS IL 101] in N,N-dimethylformamide (DMF) as dispersing phase and dodecane, ethanol and water as continuous phases. The technique yields porous, spongy, spheres with smooth surface and diameter around 1000 mu m, with morphology and chemical composition strongly affected by preparative conditions. IL loading capacity and subsequent surface topography has been investigated using optical microscopy, FT-IR, SEM, EDX, TGA and SDT. (C) 2012 Elsevier B.V. All rights reserved.