The main underlying principle behind the application of reactive distillation (RD) for selectivity enhancement is to facilitate the separation of selected components and favorably manipulate the composition profiles in the reactive zone to expedite the desired reaction. In this paper, a geometric approach of attainable region (AR), which is already developed for conventional reactor network, is extended further to include few representative RD configurations. We define new RD building blocks and the corresponding composition vectors that indicate a need of networking of RD units among themselves and with conventional reactors to enlarge the set of attainable compositions. A model reaction scheme of van de Vusse type (A -> B-k1 -> C-k2, 2A -> D-k3) is studied as an illustrative example and an algorithm is developed to obtain the attainable region for the given kinetics, feed composition and relative volatilities. In almost all the different cases, which are studied by varying the kinetics and volatility pattern, network consisting of RD units performs better than the conventional reactor network. (C) 2011 Elsevier Ltd. All rights reserved.