The Petlyuk configuration represents an attractive alternative to the simple distillation column sequences because of its potential in energy saving. This point was extensively discussed for three-component mixtures. Moving to quaternary mixtures the complexity of the Petlyuk configuration represents the main barrier of its possible implementation in the industrial practice. In the present work, a set of new alternative distillation configurations to the four-component Petlyuk is presented. A hydrocarbon and an alcohol mixture are considered to prove their applicability. The total annual cost, together with the thermodynamic efficiency and the carbon dioxide emissions, are considered as comparison index between the Petlyuk and the alternative configurations. The results obtained proved that for the cases considered at least one of the alternative configurations showed a better or at least the same performance of the Petlyuk arrangement. For this reason, the new configurations are worth of consideration when four-component mixtures are considered.