Abstract The impact of energy production, transformation and use on the environmental resources encourage to understand the mechanisms of resource degradation and to develop proper analyses to reduce the impact of the energy systems on the environment. At the technical level, most attempts for reducing the environmental impact of energy systems focus on the improvement of process efficiency. One way toward an integrated approach is that of adopting exergy analysis for assessing efficiency and test improving design and operation solutions. The paper presents an exergy based analysis for improving efficiency and safety of energy systems, named Thermorisk analysis. The purpose of the Thermorisk analysis is to supply information to control, and eventually reduce, the risk of the systems (i.e. risk of accidents) by acting on the thermodynamic parameters and safety characteristics in the same frame. The proper combination of exergy and risk analysis allows monitoring the effects of efficiency improvement on the safety of the systems analyzed. A case study is presented, showing the potential of the analysis to identify the relation between the exergy efficiency and the risk of the system analyzed, and the contribution of inefficiencies on the safety of the process. Possible modifications in the process are indicated to improve the safety of the system.