Ionic liquid with a single hydroxyl group, 1-(2-hydroxyl-ethyl)-3-methylimidazolium bromide (HEMIMB), was prepared. It was found that HEMIMB could be an efficient catalyst for CO2 cycloaddition to propylene oxide to produce propylene carbonate (PC). An ionic liquid polymer with multi-hydroxyl groups poly(1-2-hydroxyl-ethyl)-3-vinylimidazolium bromide (PHEVIMB) was also prepared. In this study, both catalytic reaction performances of HEMIMB and PHEVIMB were investigated. Results showed that product separation and catalyst recycles in the process of PHEVIMB catalytic reaction system was much more efficient with a yield of 55.5%, even after three consecutive catalyst reuses. Meanwhile, the separation was less time-efficient for homogeneous catalytic system of HEMIMB molecules with a single hydroxyl group despite of a yield of 92.4%. When it comes to practical industrial process design, the single component with multifunctional ionic liquid polymer, as catalyst, may be considered effective and friendly process.