The rising concentration of CO₂ in the atmosphere is approaching critical levels, posing a significant threat to life on Earth. Porous carbons derived from biobased materials, particularly waste byproducts, offer a viable solution for selective CO₂ adsorption from large-scale industrial sources, potentially mitigating atmospheric CO₂ emissions. In this study, we developed highly porous carbons from lemon peel waste through a two-step process, consisting of temperature pretreatment (500 °C) followed by chemical activation by KOH at 850 °C. The largest specific surface area (2821 m²/g), total pore volume (1.39 cm³/g), and micropore volume (0.70 cm³/g) were obtained at the highest KOH-to-carbon ratio of 4. In contrast, the sample activated with a KOH-to-carbon ratio of 2 demonstrated the greatest micropore distribution. This activated biocarbon exhibited superior CO₂ adsorption capacity, reaching 5.69 mmol/g at 0 °C and 100 kPa. The remarkable adsorption performance can be attributed to the significant volume of micropores with diameters smaller than 0.859 nm. The Radke–Prausnitz equation, traditionally employed to model the adsorption equilibrium of organic compounds from liquid solutions, has been shown to be equally applicable for describing the gas–solid adsorption equilibrium. Furthermore, equations describing the temperature dependence of the Radke–Prausnitz equation’s parameters have been developed.