Exergy Life Cycle Assessment (ELCA) is proposed by literature to account for the exergy embodied in products of energy systems. In order to make results of ELCA comparable, supply chains that support the life cycle of the system should be analyzed through a unified model: this is one of the main concerns related to Life Cycle Assessment and Industrial Ecology disciplines. In this paper, Hybrid Input-Output analysis is proposed as the computational structure of ELCA: according to this method, national supply chains are modeled through the Monetary Input Output Tables (MIOTs) of national economies, a constantly updated and freely available data source. Then, the adopted national MIOT is expanded to include the detailed model of the considered energy system, hence defining a Hybrid Input-Output model. The (non-renewable) exergy embodied in electricity production and the Exergy Return on Investment (ExROI) are defined as the appropriate performance indicators based on ELCA. The introduced model is here adopted for the analysis of a Waste-to-Energy (WtE) power plant currently operating in the Italian context. It is found that the primary non-renewable exergy embodied in electricity produced by the analyzed WtE is non-negligible for both the construction (127.1 toe) and the operation phases (11.6 toe/y). Nonetheless, the plant is able to produce a net amount of electricity that pays back such primary non-renewable resources requirements about a hundred times. Finally, the joint application of Exergy Analysis and ELCA lead to improve the overall thermodynamic performances of the WtE system, increasing its exergy efficiency by 1%, and reducing the non-renewable exergy embodied in electricity production by 7938 toe. [ABSTRACT FROM AUTHOR]