Abstract: There is disclosed a method of recovery of isoprene from a hydrocarbon stream consisting of predominately C-5 hydrocarbons and containing isoprene, n-pentane and other 5 carbon atom hydrocarbons which comprises subjecting said hydrocarbon stream to two successive high efficiency distillations, the first distillation being conducted in a manner as to remove as an overhead fraction, hydrocarbon components of said stream which are more volatile than the azeotrope of isoprene/n-pentane and as a bottom fraction the other hydrocarbons in said stream, subjecting the bottom fraction from the first distillation to the second distillation, the second distillation being conducted in a manner as to remove the azeotrope of isoprene/n-pentane as an overhead fraction and as a bottom fraction the other hydrocarbons which are less volatile than the azeotrope of isoprene/n-pentane, and recovering the isoprene/n-pentane azeotrope.