Reactive distillation (RD) has already demonstrated its potential to significantly increase reactant conversion and the purity of the target product. Our work focuses on the application of RD to reaction systems that feature more than one main reaction. In such multiple-reaction systems, the application of RD would enhance not only the reactant conversion but also the selectivity of the target product. The potential of RD to improve the product selectivity of multiple-reaction systems has not yet been fully exploited because of a shortage of available comprehensive experimental and theoretical studies. In the present article, we want to theoretically identify the full potential of RD technology in multiple-reaction systems by performing a detailed optimisation study. An evolutionary algorithm was applied and the obtained results were compared with those of a conventional stirred tank reactor to quantify the potential of RD to improve the target product selectivity of multiple-reaction systems. The consecutive transesterification of dimethyl carbonate with ethanol to form ethyl methyl carbonate and diethyl carbonate was used as a case study.