This article aims to present an evaluation of the environmental performance of a combustion polygeneration plant fed with lignocellulosic material from cardoon (Cynara cardunculus L.) through the technique of Life Cycle Assessment (LCA). The system boundaries encompassed macro-phases of crop production, transportation, and polygeneration processes that were able to produce 100 kW of electricity, a residual thermal energy recovery system and district heating and cooling with 270 kW of heating, and a 140 kW of cooling. The LCA was performed using Cumulative Energy Demand and ReCiPe Life Cycle Impact Assessment methods through midpoint and endpoint indicators. From 2000 h/year, 165.92 GJ of electricity and 667.23 GJ of primary energy were consumed, and 32.82 tCO2eq were emitted. The rates of Greenhouse Gas (GHG) and energy demand per MJ produced were 0.08 MJSE/MJPD, 0.30 MJPE/MJPD, and 0.01 kgCO2eq/MJPD. According to the ReCiPe method, the impact categories with the highest impact loads were Terrestrial ecotoxicity (2.44%), Freshwater ecotoxicity (32.21%), Marine ecotoxicity (50.10%), Human carcinogenic toxicity (8.75%), and Human non-carcinogenic toxicity (4.76%). Comparing the same energy outputs produced by Italian power and gas grids, the proposed polygeneration plant was able to reduce primary energy demand and GHG emissions by 80 and 81%, respectively, in addition to reducing the emissions of the five main categories of impacts by between 25 and 73%.