We report here novel dual-SO3H-functionalized heteropolyacid-based solid acids (HPA-ILs) with different Keggin heteropolyacid anions and investigate their catalytic applications in hydrolysis of cyclohexyl acetate to cyclohexanol. Compared with a variety of the traditional acidic catalysts, [Bis-Bs-BDMAEE]HPMo12O40 displayed the higher catalytic acidities and good repeated utilization. The effects of various parameters including reaction temperatures, catalysts dosage, initial reactants volume ratio, and reaction time on the hydrolysis of cyclohexyl acetate were studied in detail. The optimal condition was obtained, and the cyclohexyl acetate conversion reached up to 90.56% with 94.86% selectivity for cyclohexanol. More interestingly, the reusability of [Bis-Bs-BDMAEE]HPMo12O40 was good because it was reused five times without a significant loss in catalytic activity.