The activation mechanism of the CO₂/propylene oxide coupling catalysed by a bicomponent organocatalyst combining the use of TBABr with (multi)phenolic or fluorinated hydrogen bond donors (HBDs) was investigated using Density Functional Theory (DFT). Thus, it was shown that increasing the number of electron withdrawing trifluoromethyl substituents in HBDs strengthens their proton donor capability and allows a better stabilization by hydrogen bonding of the intermediates and transition states. In addition, the high efficiency of fluorinated monoalcohol activators is related to a dual hydrogen bonding mechanism by two fluorinated molecules that cooperatively contribute to the CO₂/propylene oxide coupling.