Abstract: An ionic liquid was synthesized with anhydrous aluminum chloride and amine hydrochloride with the mole ratio of 2∶1. The isomerization of n-hexane catalyzed by the ionic liquid was investigated. The results indicate that the ionic liquid can catalyze the isomerization of n-hexane, but it requires long reaction time. The influence of initiators including n-butanol, i-butene, i-butane and i-pentane on the isomerization of n-hexane was investigated. The conversion of n-hexane, the yield of liquid components and the selectivity of isoparaffins are 84.54%, 80.08% and 94.74%, respectively, when i-pentane is used as the initiator. This shows that i-pentane is a good initiator for the isomerization of n-hexane. The dosage of ipentane shows great influence on the isomerization of n-hexane, and the suitable dosage is 30%. The initiator i-pentane can greatly accelerate the rate of the isomerization of n-hexane. The reaction time can be shortened from 6h to 45min to achieve the similar reaction extent.