Abstract A crucial step in achieving the Net-Zero Emissions Scenario goals is thought to be integrating CO2 capture technologies into Bio-Combined Heat and Power (Bio-CHP) facilities. The present study investigates the environmental impact of a Bio-CHP plant integrated with Calcium Looping (CaL) CO2 capture through Life Cycle Assessment (LCA) methodology, comparing it with a state-of-the-art Mono-Ethanol-Amine (MEA) based CO2 capture. The environmental performance of the two capture technologies is examined using a cradle-to-gate analysis based on the ReCiPe 2016 assessment method and considering three CO2 transportation scenarios, i.e., onshore pipelines (T1), onshore and offshore pipelines (T2), and onshore pipelines, liquefaction and offshore shipping (T3). The findings of the LCA study show that the first transportation case (T1) generates the best environmental results. The CO2 liquefaction and ship transportation (T3) raises the GWP impact by 313 kg CO2 eq./t CO2 captured and determines a 13-fold increase in Fossil fuel Depletion Potential (FDP) compared to T1. When comparing the two CO2 capture technologies, the CaL system exhibits better environmental performance, with ten out of eleven impact indicators showing lower values. Beyond the environmental benefits, this research demonstrates that CaL technology surpasses the amine scrubbing system in net power output (e.g., 50.6 vs. 26.6 MWe) and direct fossil emissions (e.g., −2748.2 vs. −1079.9 kg CO2/t wood), despite a higher fuel consumption (e.g., 224.7 vs. 135.3 MWLHV). These findings underscore the advantages of integrating post-combustion CO2 capture with efficient CO2 transportation strategies, paving the way for a cleaner and more sustainable heat and power sector.