A new superstructure form of heat exchanger networks (HEN) is proposed based on expert system (ES) in this paper. The new superstructure form is combined with the practical engineering. The optimal mathematical model based on exergo-economic objective function is presented too, which contains the flow exergy dissipation of HEN. Further, the strategy of decomposition & coordination is proposed to optimize network and match units. This method can deal with larger scale HEN synthesis and obtain the optimal HEN configuration automatically. Finally, a case study is presented to demonstrate the effectiveness of the method.