The invention relates to extractive distillation compositions for separating a mixture of hydrocarbon compounds, wherein the extractive distillation composition includes at least one alkylene glycol compound, and at least one compatibility agent, wherein the compatibility agent is selected from materials having polar parameters and hydrogen bonding parameters such that the extractive distillation composition provides improved separation of the hydrocarbon compounds, as compared to the use of the extractive distillation composition without the compatibility agent.