In this work, we present a methodology for the global optimization of reactive distillation (RD) networks, through the Infinite DimEnsionAl State-space (IDEAS) approach. Within the IDEAS framework, network synthesis is formulated as an infinite dimensional linear optimisation problem. The IDEAS conceptual framework is realized through solution of a series of finite dimensional linear programs whose optimum values converge to the infinite program's infimum. The proposed optimal design methodology is demonstrated on a case study involving reactive distillation-based synthesis of methyl tert-butyl ether (MTBE) from isobutene and methanol. (C) 2004 Elsevier Ltd. All rights reserved.