With the constant increase of energy costs and environmental impacts, improving the process efficiency is considered a priority issue for the manufacturing field. A wide knowledge about materials, energy, machinery, and auxiliary equipment is required in order to optimize the overall performance of manufacturing processes. Sustainability needs to be assessed in order to find an optimal compromise between technical quality of products and environmental compatibility of processes. In this new Industry 4.0 era, innovative manufacturing technologies, as the additive manufacturing, are taking a predominant role. The aim of this work is to give an insight into how thermodynamic laws contribute at the same time to improve energy efficiency of manufacturing resources and to provide a methodological support to move towards a smart and sustainable additive process. In this context, a fundamental step is the proper design of a sensing and real-time monitoring framework of an additive manufacturing process. This framework should be based on an accurate modelling of the physical phenomena and technological aspects of the considered process, taking into account all the sustainability requirements. To this end, a thermodynamic model for the direct laser metal deposition (DLMD) process was proposed as a test case. Finally, an exergetic analysis was conducted on a prototype DLMD system to validate the effectiveness of an ad-hoc monitoring system and highlight the limitations of this process. What emerged is that the proposed framework provided significant advantages, since it represents a valuable approach for finding suitable process management strategies to identify sustainable solutions for innovative manufacturing procedures.