In this paper, a novel method to deal with the design and the synthesis of finishing reactive distillation columns with one reactive core, two rectifying sections, and one stripping section is presented. The attention of our work is concentrated on three subjects: (i) the feasibility of a given separation at both finite and total reflux operation; (ii) the minimum energy demand operation; (iii) the distribution of the reaction between the reactor and the finishing reactive column. The design problem presents the same grade of difficulty as that found in the design of conventional extractive columns. A geometric based method is used to explain key features of reactive distillation. Here, the relation between the reaction yield and the distillate flow rate plays a role similar to that of the entrainer flow in extractive distillation. Hence, special attention is given to the behavior of the profiles inside the rectifying section below the reactive core. The methodology is illustrated using the well-known MTBE case study.