The 2-propanol (i-PrOH) adsorption properties of InOF-1 are investigated along with the confinement of small amounts of this alcohol to enhance the CO2 capture for i-PrOH@InOF-1 (1.25-fold improvement compared to pristine InOF-1). InOF-1 exhibited a high affinity towards i-PrOH, experimentally quantified by ΔHads (-55 kJ mol-1), and DFT geometry optimisations showed strong hydrogen bonding between O(i-PrOH) and H(μ2-OH). Quantum chemical models demonstrated that the CO2 capture increase for i-PrOH@InOF-1 was due to a decrease in the void surface of InOF-1 (bottleneck effect), and the formation of essential hydrogen bonds of CO2 with i-PrOH and with the hydroxo functional group (μ2-OH) of InOF-1.