The European Union is targeting climate neutrality by 2050, with a focus on enhancing energy efficiency, expanding renewable energy sources, and reducing emissions. Within Italy’s electricity mix, bioenergy sources, namely biogas, solid biomass, and bioliquids, play a crucial territorial role. A comparative analysis was conducted through Life Cycle Assessment (LCA), utilizing national data from the ARCADIA project, to assess the environmental sustainability of the investigated bioenergy chains and identify the most convenient ones. The study revealed that, among the bioenergy sources, solid biomass emerges as the most environmentally friendly option since it does not rely on dedicated crops. Conversely, biogas shows the highest environmental impact, demonstrating less favorable performance across nine out of the sixteen evaluated impact categories. The LCA underscores that the cultivation of dedicated energy crops significantly contributes to environmental burdens associated with electricity generation, affecting both biogas and bioliquids performance. The cultivation process needs water and chemical fertilizers, leading to adverse environmental effects. These findings highlight the importance of prioritizing residual biomass for energy generation over dedicated crops. Utilizing forestry and agro-industrial residues, municipal solid waste, and used cooking oils presents numerous advantages, including environmental preservation, resource conservation and recovery, as well as waste reduction.