Here, we report the preparation of microporous-activated carbons from a Brazilian natural lignocellulosic agricultural waste, cupuassu shell, by pyrolysis at 500 ºC and KOH activation under different experimental conditions and their subsequent application as adsorbent for CO2 capture. The effect of the KOH:precursor ratio (wt/wt%) and the activation temperature on the porous texture of activated carbons have been studied. The values of specific surface area ranged from 1132 to 2486 m2/ g, and the overall micropore volume ranged from 0.73 to 1.02 cm3/ g. Carbons activated with 2:1 ratio of KOH and activation temperature of 700 ºC presented a CO2 adsorption at 1 bar of 7.8 and 4.4 mmol/g at 0 °C and 25 ºC, respectively. The isosteric heat of adsorption, Qst , was calculated for all samples by applying the Clausius–Clapeyron approach to CO2 adsorption isotherms at both temperatures. The values of CO2 adsorption capacities are among the highest reported in the literature, especially for activated carbons produced from biomass.