The transition towards energy efficiency measures and green energy sources is strongly fostered by the European Union. Italy is among the EU countries that have heavily invested in renewable energy sources, more than doubling their share in gross final energy consumption. In particular, biogas has a pivotal role in the generation of electricity and can also be upgraded into biomethane, with a higher and more stable energy content. In this study, the sustainability of the supply chain of electricity from biogas in Italy has been thoroughly analyzed in the broader framework of the ARCADIA (Life Cycle Approach in Public Procurement and Italian LCA Database for Resource Efficiency) project. The environmental assessment, carried out by means of Life Cycle Assessment (LCA), provides a two-fold perspective. Firstly, it allows us to identify the main hotspots of the investigated system, such as the cultivation of dedicated crops, and to provide useful insights for improving environmental performance. Furthermore, a focus on the modeling of the dataset related to the production of electricity from biogas within the Italian electricity mix represents a step ahead in the LCA research, filling the lack of site-specific databases for reliable LCA results.