The alkylation reaction of isobutane with 2-butene to yield C₈-alkylates was performed using Brønsted–Lewis acidic ionic liquids (ILs) comprising various metal chlorides (ZnCl₂, FeCl₂, FeCl₃, CuCl₂, CuCl, and AlCl₃) on the anion. IL 1-(3-sulfonic acid)-propyl-3-methylimidazolium chlorozincinate [HO₃S-(CH₂)₃-mim]Cl-ZnCl_{2 (x=0.67)} exhibited outstanding catalytic performance, which is attributed to the appropriate acidity, the synergistic effect originating from its double acidic sites and the promoting effect of water on the formation and transfer of protons. The Lewis acidic strength of IL played an important role in improving IL catalytic performance. A 100% conversion of 2-butene with 85.8% selectivity for C₈-alkylate was obtained under mild reaction conditions. The IL reusability was good because its alkyl sulfonic acid group being tethered covalently, its anion [Zn₂Cl₅]⁻ inertia to the active hydrogen, and its insolubility in the product. IL [HO₃S-(CH₂)₃-mim]Cl-ZnCl₂ had potential applicability in the benzene alkylation reaction with olefins and halohydrocarbons.