CO2 capture of InOF-1 was enhanced 3.6-fold, at 1 bar and 30 °C, by confining EtOH within its pores. Direct visualisation by single crystal X-ray diffraction revealed that EtOH divides InOF-1 channels in wide sections separated by "bottlenecks" caused by EtOH molecules bonded to the μ2-OH functional groups of InOF-1.