The single-step process for conversion of syngas to DME gives higher conversion than the syngas-to-methanol process. This arises because of a synergy among the three simultaneous reactions, methanol synthesis, methanol dehydration and water gas shift, in the process. This paper analyzes the role each reaction plays in the synergy using both experimental and simulated results. Under typical industrially relevant conditions using a commercially available catalyst system, the reaction system is far away from the thermodynamic equilibrium, and the rates of the reactions are the prime determinant in realizing the beneficial effects of the synergy. Furthermore, feed gas composition; strongly affects the potential benefit of the synergy on the process. The implications of this understanding for research and process applications are discussed.