Extractive distillation is a recognized useful way to separate close-boiling mixtures. Its performance is influenced by the factors such as process arrangement, tray configuration and solvent chose. The recent research development of these factors is described. Meanwhile, the application of extractive distillation in some important petrochemical areas was briefed such as desulfurization gasoline, retrofitting of aromatics separation process, separation of fluid catalytic cracking (FCC) by-product, which helps promote the grade of end products, solve some complicated engineering problems, thus brings with an obvious economic result.