This study investigated the utilization of CO2 as carbon neutral chemical feedstock in the thermo-chemical processing (i.e., pyrolysis and gasification) of biomass to enhance sustainability via modification of the composition of end products. To justify the universal function of CO2 in the thermo-chemical process, the biomass experimented on in this work was not limited to ligno-cellulosic biomass; seaweed (i.e., red macroalgae) was used to expand biofuel feedstock beyond terrestrial biomass. Our experimental results validated the achieved enhanced generation of ∼200% for H2 and ∼1000% for CO by means of adopting CO2 in the thermo-chemical process, as compared to the case in N2. This can be explained by the enhanced thermal cracking of volatile organic carbons (VOCs) evolved from the thermal degradation of biomass and the reaction between CO2 and VOCs. Considering mass balance under our experimental conditions, we confirmed reaction between CO2 and VOCs, which was universally observed in pyrolysis of all biomass samples used in this work. Thus, the identified influence of CO2 in the thermo-chemical process can be directly applied in a variety of research and industrial fields, which would be environmentally desirable.