Phasing out fossil fuels to renewables is currently a global priority due to the climate change threat. Advocacy for biomass use as an energy source requires assessing the quality biomass and ecological impacts of bioenergy supply chains. This study evaluated the quality of biomass residues from orchards and silviculture transported from different Northern and Central Italy locations and the carbon footprint of a biomass power plant. The total greenhouse emissions were calculated based on primary data for 2017 according to the ISO/TS 14067. All the residue samples showed their suitability for biofuel use. Ash content was relatively low on average (3–5% d.m.), except for grapevine residues (18% d.m.). The lower heating value was within the expected range of 15–21 MJ kg−1 for plant species. The average GHG emission from the power plant was 17.4 g CO2 eq./MJ of electrical energy, with the energy conversion (38%) and transportation of biomass (34%) phases being the main impact contributors. For this study, impacts of residual agricultural residue were about half that of residues from forest management, mainly due to chipping and greater transport distance. Results show that sourcing residual biomass materials for electricity generation close to power plants significantly reduce GHG emissions compared to conventional fossil fuels.