This paper presents a novel superstructure and optimization model for the simultaneous synthesis of process water and heat exchanger networks. This superstructure combines the water network and heat exchanger network using interconnecting hot and cold streams. The water network has been extended for both direct and indirect heat exchanges. In addition, opportunities for heat integration between hot and cold streams, splitting and mixing of the freshwater and wastewater streams are incorporated within the superstructure. The proposed model is formulated as a non-convex MINLP (mixed-integer non-linear program), where the objective is to minimize the total annual costs of the network. A new convex hull formulation is presented for identifying the streams' roles within the network. Three examples involving single and multiple contaminant problems are presented in order to illustrate the applicability and capabilities of the proposed superstructure and model. In all cases the resultant networks exhibit lower total annual costs, whilst the freshwater and utilities consumption are the same as reported in the literature. In addition, novel designs for heat-integrated process water networks with smaller or same number of heat exchangers are presented. (c) 2013 Elsevier Ltd. All rights reserved.