The ethanol production process employing lignocellulosic material (second generation ethanol-2G) is one of the remarkable proposals for the worldwide energetic security. Currently, there is a significant technical-scientific effort in order to obtain sustainable alternative routes for the production of 2G ethanol. The thermodynamic property exergy can be applied for the execution of the energetic analysis of this type of system. The analysis of the exergetic content indicates the economic value associated to the process, since it is characterized as the potential to execute work. In this sense, the exergetic analysis is applied to evaluate alternative technologies for the sustainable development, being a resource of increasing use in the literature. However, there is still a reduced amount of review articles, particularly in Brazilian literature, destined to present the application of this type of analysis to 2G ethanol production. Therefore, this article aims to exhibit some fundamental concepts about this technique, as well as indicators and analysis methods based on exergy. Besides that, applications of the technique to 2G ethanol production processes are presented, in order to highlight the applicability of the thermodynamic evaluation, exergetic analyses and methods and main diagnoses obtained by means of this technique.