Two activated carbons (AC) resulting from CO2 activation of Maize Cob Waste (MCW) were investigated as adsorbent materials for biogas upgrading to bio-methane applying a biorefinery concept. The porous carbons were originated from different times of activation and the one resulting from 3 h with CO2 (MCW(PA)3 h) showed better textural properties, higher working capacity, and selectivity towards CO2 than the carbon resulting from 2 h of activation (MCW(PA)2 h), making it the best candidate for biogas purification. The adsorption equilibrium measurements of CO2 and CH4 on MCW(PA)3 h carbon showed that the Sips isotherm model, as well as the Adsorption Potential Theory (APT), can be confidently employed to accurately correlate the adsorption equilibrium data of the adsorbates employed. In the range of the partial pressures typical for biogas upgrading units, MCW(PA)3 h showed higher CO2 uptakes than the ones reported for coal-based commercial ACs and similar uptakes to the ones reported for bio-based ACs. Moreover, the axial dispersed plug-flow and Linear Driving Force (LDF) approximation for lumped solid-diffusion mass transfer model used for the prediction of the dynamic behaviour of the adsorbate-adsorbent system, provided a good agreement with the experimental results, demonstrating its applicability to the studied system. This work represents the basis of future modelling works of a Pressure Swing Adsorption (PSA) cycle based on the use of MCW(PA)3 h as adsorbent material and demonstrates the high potential of this novel material to be applied in biogas upgrading processes