This work evaluates the feasibility to separate selectively lithium cations from complex aqueous solutions containing sodium, cobalt and nickel ions using a supported liquid membranes (SLMs) impregnated with a mixture of hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(4)mim][NTf2]) and tri-n-butyl phosphate (TBP) as the carrier. Various hydrophobic room-temperature ionic liquids (ILs), namely with dialkyl imidazolium, quaternary ammonium and phosphonium cations, were tested as supporting phase in hydrophobic porous polyvinylidene fluoride (PVDF) membranes. Membrane impregnation studies show that the mass uptake is following the density of the organic phase. The stability experiments indicate that the losses of IL in the surrounding aqueous phases are related to its aqueous solubility and could be reduced by the addition of salt in the feed and/or stripping phase. Lithium membrane extraction and selective separation from aqueous complex solutions containing large amounts of sodium ions has been demonstrated. The selective separation of lithium from cobalt and nickel ions as well as from magnesium in acidic aqueous solutions has shown promising results. The results obtained in present study indicate that the use of hydrophobic IL for SLM preparation allows the facilitated transport of lithium ions.