Reactive distillation is one of the most attractive reactive separations, combining chemical reaction with the separation of chemicals, leading to new processes providing higher economy. This work investigates the sustainability of those process systems, which incorporate reactive distillation, through the use of Life Cycle Thinking via Life Cycle Assessment. Moreover we use economic and environmental metrics. The proposed decision support strategy is exemplified in the case of the synthesis of isopropyl myristate production using a reactive distillation column and a homogenous catalyst.