The possibility of using room-temperature ionic liquids (RTILs) in bulk (nonsupported) and supported liquid membranes for the selective transport of organic molecules is demonstrated. A systematic selective transport study, in which 1,4-dioxane, propan-1-ol, butan-1-ol, cyclohexanol, cyclohexanone, morpholine, and methylmorpholine serve as a model seven-component mixture of representative organic compounds, and in which four RTILs based on the 1-n-alkyl-3-methylimidazolium cation (n-butyl, n-octyl, and n-decyl) are used together with the anions PF(6)(-) or BF(4)(-), immobilized in five different supporting membranes, confirms that the combination of the selected RTILs with the supporting membranes is crucial to achieve good selectivity for a specific solute. The use of the RTIL 1-n-butyl-3-methylimidazolium hexafluorophosphate, immobilized in a polyvinylidene fluoride membrane, allows an extremely highly selective transport of secondary amines over tertiary amines (up to a 55:1 ratio). The selective transport of a given solute through the RTIL/membrane system results from the high partitioning of the solute to the liquid membrane phase which, in the case of amines, is rationalized mainly by the formation of a preferential substrate/H[bond]C(2) hydrogen bonding to the imidazolium cation.