Conversion of biomass into gasoline of high octane number is challenging. In this study, conversion of biomass-derived γ-valerolactone into gasoline was achieved by decarboxylation of valerolactone to produce butenes and alkylation of the produced butenes with butane using [CF₃CH₂OH₂][CF₃CH₂OBF₃] as an efficient catalyst. The obtained gasoline was rich in trimethylpentane with a high research octane number of 95.4.