Ionic liquids (ILs) are a new class of liquid solvent, whose use has led to a green chemical revolution because of their unique array of physico-chemical properties, headed by their negligible vapour pressure and their exceptional ability to stabilize biocatalysts. Hydrophobic ILs based on cations with long alkyl side-chains, e.g. N,N,N,N-hexadecyltrimethylammonium bis(trifluoromethylsulfonyl)imide([C(16)tma][NTf2]), are temperature switchable ionic liquid/solid phases that behave as sponge-like systems(sponge-like ionic liquid, SLILs). Based on this new property, SLILs have been used to develop straight-forward and clean approaches for producing nearly pure synthetic compounds with added value (e.g. geranyl acetate, anisyl acetate, methyl oleate, etc.) in two steps: an enzymatic synthetic step as liquid phase, and then a product separation step involving simple centrifugation as a solid phase. (C) 2014 Elsevier B.V. All rights reserved.