Due to its high reactivity, monochloroacetic acid (MCA) is an essential intermediate used in the manufacturing of a wide variety of chemicals. Its industrial production process is highly energy- and capital-intensive, requiring costly purification steps to remove dichloroacetic acid (DCA) impurities. Here, an innovative eco-efficient process for MCA-DCA separation is proposed based on extractive distillation in a fully thermally coupled system (a dividing-wall column (DWC) or an equivalent side-rectifier configuration) using a new effective solvent: diethylene glycol dipentylether. The design was optimized by performing sensitivity analyses and varying key operating and design parameters. The study proves that separating MCA-DCA by an extractive DWC (or thermally coupled) is feasible, efficient, controllable, economic, and sustainable.