BACKGROUND The transesterification of methyl acetate and isoamyl alcohol catalyzed by ionic liquids is a new environment-friendly method for isopentyl acetate (iso-AmAc) production, and also appropriate for the recovery of polyvinyl alcohol (PVA) byproducts. Therefore, it is of great significance for iso-AmAc production from PVA byproducts to explore alternative processes with the goal of improving the conversion of the chemical equilibrium reaction and energy efficiency, including reactive distillation (RD), dividing-wall reactive distillation (RDWC) and pervaporation (PV)-based hybrid reactive distillation. RESULT This article proposed four novel reactive hybrid processes with feedstock of mixed PVA byproducts and made a comparison with two conventional processes of RD and RDWC in terms of the minimum total annual cost (TAC) and CO2 emissions. The results revealed that the RDWC-PV can give a 35.61% saving in TAC and a 40.27% reduction in CO2 emissions compared with the RD, and the other three RD-PV hybrid processes have less CO2 emissions and equivalent TAC compared with the RDWC. CONCLUSION In summary, all hybrid processes proposed were more energy-saving and economical than the conventional RD, especially the RDWC-PV, due to synergistic advantages of various process intensification methods. (c) 2018 Society of Chemical Industry