Biochar is widely used for various environmental remediation strategies such as soil amendment because of its intrinsic carbon negativity and porosity. Biochar is a charcoal-like material produced via pyrolysis of biomass. To determine an effective method for modification of the porosity and morphology of biochar and establishment of a more sustainable pyrolysis platform for biomass valorization, this study used CO2 as a reactive gas medium in the biomass pyrolysis process. This study placed emphasis on elucidating the role of CO2 in the production of biochar from different types of biomass, such as cellulose, xylan, lignin, grass, and oak wood. The surface area and porosity of biochar were strongly related to the type of biomass. Under comparable pyrolysis conditions, the surface area of biochar decreased in the following order: cellulose > xylan > lignin ∼ oak wood > grass. The use of CO2 as the gas medium in biomass pyrolysis affected the surface area and porosity of biochar samples derived from biomass feedstock. For instance, the surface area and total pore volume of the oak-wood-derived biochar produced in the CO2 environment were twice those produced in the N2 environment. Given that the increases in the biochar surface area and porosity were attributed to the enhanced release of volatile organic compounds (VOCs) from biomass, CO2 may have enhanced VOC release (removal) during pyrolysis. Therefore, the use of CO2 in a pyrolysis platform is expected to be a strategic approach for biomass valorization.