This article evaluates the processing of Municipal Solid Waste (MSW) and its contribution to sustainability from the viewpoint of its net exergy balance. The evaluation follows the recent framework for estimation of Exergy Footprint and Exergy Profit for a given Process System. The method evaluates the Exergy Assets and Liabilities, estimating the Exergy Profit as the balance of these two. The concept of avoided exergy by substituting the useful chemical to its primary production, similar to the concept of avoided emission is also proposed in this work. The obtained estimate is the specific contribution of the considered MSW processing system. For estimating the overall impacts, the obtained Exergy Profit has to be added to the contributions of the potential upstream and downstream processes. The results show the potential value that can be obtained and sustainability contribution to be achieved by the extraction of useful chemicals from waste and waste-to-energy conversion. The chemical extraction option shows a marginally higher Exergy Profit compared with the typical MSW incineration practice, indicating that, as long as there is a sufficient market demand for the chemical products, this route can be more beneficial. An important outcome is that the product substitution can lead to three-fold increase in the Exergy Profit and the related emission savings.