In this work, dicationic acidic heteropolyanion-based ionic liquids were synthesized, and used in transesterification reaction of methyl acetate with isooctyl alcohol for producing isooctyl acetate. Compared with H2SO4, and H3PW12O40, [Bis-BsImB][HPW12O40] and [Bis-Bs-DABCO][HPW12O40] shown excellent catalytic performance. The reaction kinetics and chemical equilibrium of the transesterification catalyzed by [Bis-BsImB][HPW12O40] and [Bis-Bs-DABCO][HPW12O40] were investigated. The effects of reaction temperature, initial reactant molar ratio, and catalyst concentration on the kinetics were studied in detail. The kinetic data were successfully correlated by a pseudohomogeneous model in the temperature range of 328.15 - 343.15 K. The simulation values obtained by the kinetic model were in good agreement with the experimental data. Moreover, [Bis-BsImB][HPW12O40] and [Bis-Bs-DABCO][HPW12O40] could be easily recovered and reused five times without any obvious decrease in catalytic activity.