The reactive distillation process regarding ionic liquid-catalyzed transesterification for iso-pentyl acetate production is attracting increasing attention owing to outstanding properties of green homogeneous catalysts. This work investigates the economics and controllability of conventional reactive distillation (CRD) and dividing-wall reactive distillation (RDWC) configurations for this reaction. The optimizations of both configurations are carried out based on the minimum total annual cost (TAC) by the sequential iterative procedures. Their effective control structures are proposed and verified when either feed flow or feed composition disturbances are introduced. The results show that the RDWC process permits the reduction of up to 22.8% in the TAC compared to the CRD process. Furthermore, it is justified in view of the integral squared errors calculated that both control structures represent good dynamic performances in regard to resisting two kinds of feed disturbances.