In this work, the potential of monohydrate Lithium hydroxide (LiOH) as a high capacity adsorbent for CO2 capture was investigated experimentally and theoretically. The effects of operating parameters, including temperature, pressure, LiOH particle size and LiOH loading, on the CO2 capture in a fixed-bed reactor have been experimentally explored using response surface methodology (RSM) based on central composite design. The optimum conditions obtained by the RSM for temperature, pressure, mesh and maximum adsorption capacity were calculated as 333 K, 4.72 bar, 200 micron and 559.39 mg/g, respectively. The experiments were evaluated using isotherm, kinetic and thermodynamic modeling. Isotherm modeling showed that Hill model could deliver a perfect fit to the experimental data, based on the closeness of the R2-value to unity. The kinetics models showed that the process was chemical adsorption and obeyed the second order model. In addition, thermodynamic analysis results showed that the CO2 adsorption was spontaneous and exothermic in nature. In addition, based on the density functional theory, we investigated the chemical stability of LiOH atomic clusters and examined the effects of LiOH nanonization on the physical attraction of carbon dioxide.