Abstract In this paper, a new formulation based on disjunctive programming to model the superstructure of alternative configurations for the synthesis, design and analysis of combined cycle power and desalination plant recently developed in Mussati et al. [Desalination, 182 (2005) 123–129] is presented. In this new formulation, boolean variables model discrete decisions while continuous variables represent the operation conditions of the process, e.g., flow rates, energy demand. Optimal unit configuration and operating conditions are computed by solving the proposed model in order to satisfy electricity generation and freshwater productions demands. Rigorous, non-convex and highly non-linear constraints are involved in the formulation, therefore, robust and efficient solution algorithms have to be used. The Logic-Based Outer Approximation (LOA) algorithm developed by Turkay and Grossmann [Comp. Chem. Eng., 20 (8) (1996) 959] with the modifications introduced by Yeomans and Grossmann [Ind. Eng. Chem. Res., 39 (6) (2000) 1637] are used as part of the solution procedure. The model is implemented and solved in the General Algebraic Modeling System (GAMS). Several study cases for different required power to water ratios are presented and analyzed in order to illustrate the robustness and computational performance of the proposed model.