The Petlyuk arrangement is the mostly studied thermally coupled configuration due to its minimum energy requirement for multicomponent distillation. In this paper, a new method for synthesis of thermodynamically equivalent structures (TES) for the Petlyuk arrangement is presented. The total number of the possible TESs is theoretically calculated with a derived formula a priori. Then, a simple procedure is formulated which generates all of the TESs step-by-step. It is shown that the new method can systematically produce all the known TESs as well as the missing ones for the Petlyuk arrangement of any n-component mixture. It is found that, for any n-component mixture, the Petlyuk arrangement can produce a unique thermodynamically equivalent side column structure by simultaneously moving all of its movable column sections. It constitutes a new mechanism to derive the satellite column superstructure with one reboiler and one condenser. Finally, it is concluded that the Petlyuk arrangement is a superstructure that incorporates all of the known structures as its substructures.