The CO2 capture performance of InOF-1 was optimised by confining small amounts of MeOH within its micropores (MeOH@InOF-1). In comparison with fully activated InOF-1, MeOH@InOF-1 shows a 1.30 and 4.88-fold increase in CO2 capture capacity for kinetic and static isothermal CO2 adsorption experiments respectively. Density functional theory calculations coupled with forcefield based-Monte Carlo simulations revealed that such an enhancement is assigned to an increase of the degree of confinement felt by the CO2 molecules resulting from the formation of a lump at the vicinity of the μ2-OH groups since MeOH strongly interacts with these adsorption sites and is thus highly localized in this region.