In the current styrene production process the distillation of the close-boiling ethylbenzene/styrene mixture to obtain an ethylbenzene impurity level of 100 ppm in styrene accounts for 75-80% of the energy requirements. The future target is to reach a level of 1-10 ppm, which will increase the energy requirements for the distillation even further. Extractive distillation is a well-known technology to separate close-boiling mixtures up to high purities. The objective of this study was to investigate whether extractive distillation using ionic liquids (ILs) is a promising alternative to obtain high purity styrene. Three ILs were studied: [3-mebupy] [B(CN)(4)], [4-mebupy] [BF4], and [EMIM] [SCN]. Extractive distillation with sulfolane and the current conventional distillation process were used as benchmark processes. The IL [4-mebupy][BF4] is expected to outperform the other two ILs with up to 11.5% lower energy requirements. The operational expenditures of the [4-mebupy][BF4] process are found to be 43.2% lower than the current distillation process and 5% lower than extractive distillation with sulfolane extractive distillations. However, the capital expenditures for the sulfolane process will be about 23% lower than those for the [4-mebupy][BF4] process. Finally, the conclusion can be drawn from the total annual costs that all studied extractive distillation processes outperform the current distillation process to obtain high purity styrene, but that the ILs evaluated will not perform better than sulfolane. (C) 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.