The alternative fuel, dimethyl ether (DME), which can be synthesized from natural gas, coal or biomass syngas, has been traditionally used as a diesel substitute or additive. DME purification processes with a conventional distillation sequence consume a large amount of energy. We used dividing wall columns (DWCs) to improve the energy efficiency and reduce the capital cost of the DME purification process. Various possible DWC arrangements were explored to find the potential benefits derived from thermally coupled distillations. The results show that utilizing DWCs can significantly reduce both the energy consumption and investment cost of the DME purification process. The lower energy consumption also results in the reduction of the CO2 emission.