The capture of CO2 by biochar has recently become one of the cornerstones of circular economy models for a sustainable society. In this work, we synthesized an activated biocarbon using Trametes gibbosa (BioACTG) in a one-step synthesis. We investigated CO2 adsorption mechanisms under five different temperatures using a statistical physics approach. The data was better represented by the multilayer model with two distinguished energies, providing more accurate values for the estimated parameters. According to the number of carbon dioxide molecules per site (n) and the densities of the receptor sites (Dzif), the tendency to form a second layer increased as the temperature increased. The adsorption of CO2 on BioACTG was exothermic (the values of Qasat = 15.5 mmol/g at 273 K decrease to 10.5 mmol/g at 353 K), and the temperature influenced CO2 as well as the morphological features of the process. A computational approach was used to investigate the electronic properties of the adsorbate, showing that its lowest unoccupied orbital (LUMO) heavily contributed to the high efficiency of the process which was ruled by pore diffusion mechanisms driven by energetic fluctuations. Other molecules present in CO2-rich mixtures were also investigated, showing that their concentration limited their competitiveness with CO2. Adjusted isotherms of CO2 adsorbed onto BioACTG by the multilayer model with saturation. Display omitted •BioACTG uptake of CO2 occurred in multilayer.•Temperature highly influenced the adsorbate energetic distributions.•The morphological features of the adsorbent varied as temperature increased.•Pore diffusion was driven by LUMO.•Competitive effects would only be significant in high concentration.