EtOH sorption properties were investigated in MIL-53(Al)-TDC and found a strong interaction between EtOH and the MOF material (ΔHads = 69.6 kJ mol-1). CO2 capture was enhanced upon confining small amounts of H2O. Upon confining small amounts of EtOH however, the CO2 uptake was not improved. The difference in CO2 uptake with EtOH and H2O was rationalised using computational calculations. The analysis of the quantum theory of atoms in molecules (QTAIM) showed a covalent interaction between a MOF model and confined molecules (EtOH and H2O), and no difference in the hydrogen bonds between confined molecules and CO2.