In this work, a novel energy-efficient distillation technology combining reactive dividing-wall column (RDWC) with vapor recompression heat pump (VRHP) is proposed. The integrated RDWC with VRHP models with intermediate reboiler or bottom reboiler are designed for reaching better energy-savings and economic performance. The results showed that the reactive dividing-wall column with vapor recompression heat pump and intermediate reboiler is more attractive than the reactive dividing-wall column with vapor recompression heat pump and bottom reboiler in this study. Adding a preheater to the reactive dividing-wall column with vapor recompression heat pump and intermediate reboiler (RDWC-VRHP-IR2) can further reduce the compression ratio and reach better performance. The RDWC-VRHP-IR2 saves 57.06% of total utility consumption, 31.31% of total annual cost with the payback period of 5 years, and 61.52% of CO2 emissions compared with the conventional two-column reactive distillation system.