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In this work, aqueous pentaethylenehexamine (PEHA) was studied as a solvent for CO2 removal to produce purified bio-syngas from biomass gasification, but also as a first step towards negative carbon emissions applying carbon capture and storage (CCS) technologies. Capture of CO2 was tested both with synthetic gas (lab-scale) and real syngases from the pilot-scale gasifier fed with a wide range of forest-based biomasses. The results showed that the effects of the components other than CO2 and the impurities from the real syngas on the performance of PEHA for CO2 removal are negligible. Combined with previous research results from lab-testing with pure CO2 absorption, the aqueous PEHA was shown to be a promising solvent for CO2 removal from syngas. PEHA was also tested as a biomass pre-treatment agent to improve gasification behavior, however, no significant improvement could be identified during the tests performed in this study.