Abstract: A diolefin (isoprene or butadiene) is separated from a mixture thereof with other hydrocarbons by feeding the mixture to an extractive distillation column at a point intermediate its ends and also feeding to that column, at a point adjacent its upper end, an imidazole derivative, such as N-methyl imidazole, which is a solvent for the diolefin, withdrawing substantially all of the other hydrocarbons from the upper end of the column and withdrawing the solvent, substantially all of the diolefin and the balance of the other hydrocarbons as bottom product from that first extractive distillation column. That bottom product is then fed to a second extractive distillation column, the diolefin is withdrawn from its upper end in substantially pure form, the balance of the other hydrocarbons are withdrawn in vapor phase and the solvent is withdrawn from the lower end of the second extractive distillation column for recycle to the first and second extractive distillation columns.