Activated carbons represent one of the important categories of the adsorbent materials for CO2 capture currently under development. However, the low adsorption capacity and selectivity at low CO2 partial pressure or relatively high flue gas temperatures is the main barrier for carbons to be applied in post-combustion CO2 capture under practical conditions. Here, we report the successful preparation of hierarchical ultra-micro/mesoporous bio-carbons from using a facile one-step method with a low-grade biomass waste as the feedstock. The bio-carbons exhibit high adsorption capacities (1.90 mmol/g) and record-high Henry’s law CO2/N2 selectivities up to 212 at ambient temperature and low CO2 partial pressure. Unlike conventional chemical activation process for manufacturing carbon materials, the integrated compaction-carbonization-activation method proposed endows the biowaste-derived carbons with unique hierarchical bio-modal pore structures, which is highly characterised by their high mesoporosity and high ultra-microporosity with narrow pore size distributions. The results demonstrated that the unique surface textural properties along with the enhanced surface chemistry due to the simultaneously achieved potassium intercalation created favourable conditions for CO2 adsorption with high CO2/N2 selectivity at low CO2 partial pressures, whilst the presence of mesoporosity greatly increased the CO2 adsorption kinetics. Measurements of CO2 adsorption heat confirmed the strong surface affinity of the prepared bio-carbons to CO2 molecules.