The CO₂ separation performance has been explored under dry and pre-humidified conditions for the fluorinated metal organic frameworks SIFSIX-Ni-pyr, ALFFIVE-Ni-pyr, SIFSIX-Ni-bipyr and ALFFIVE-Ni-bipyr, which are incorporated with/without a coordinatively unsaturated site (CUS), Al, and organic linkers 1,4-pyrazine and 4,4′-bipyridine. The ultra-small pore size (∼4 Å) of the pyrazine analogues of fluorinated-MOFs, i.e. SIFSIX-Ni-pyr and ALFFIVE-Ni-pyr, showed infinite selectivity towards CO₂ with low uptake capability under dry conditions, which drastically reduced to 0 wt% under very low pre-humidification conditions (∼10–15 wt% adsorbed moisture). In marked contrast, the bipyridine analogues SIFSIX-Ni-bipyr and ALFFIVE-Ni-bipyr showed significant CO₂ capture performance of up to 30–40 wt% with pre-humidification. Further, both SIFSIX-Ni-bipyr and ALFFIVE-Ni-bipyr showed high CO₂ selectivity as well as good working capacity at 1–10 bar while poor selectivity is observed for the pyrazine analogues with pre-humidification. The incorporation of Al as a CUS provides stability to the ALFFIVE-Ni-bipyr fluorinated-MOF under pre-humidified conditions due to the ability of Al to co-ordinate with water molecules in hydrogen bonded networks. Therefore, to develop physisorption-based CO₂ capturing processes under pre-humidified conditions, the use of Al incorporated ALFFIVE-Ni-bipyr is highly suitable, which may outperform most of the fluorinated-MOFs and other classes of porous solids reported so far.