A flexible dipyridyl ligand 1,2‐bis(4‐pyridylmethylamino)ethane (L) was synthesized and its diverse coordination mode with Zn(II) and Cd(II) in presence of different dicarboxylate renders five novel Metal–Organic Frameworks, namely, {[Zn(L)(BDC)]⋅6.5H2O}n (1), {[Zn(L)(NH2‐BDC)]⋅6.5H2O}n (2), {[Cd(L)(NH2‐BDC)]⋅7H2O}n (3), {[Cd(L)(OH‐BDC)]⋅H2O}n (4), and {[Cd(L)(diOH‐BDC)]⋅2H2O}n (5) (where, L= 1,2‐bis(4‐pyridylmethylamino)ethane and BDC=benzene‐1,4‐dicatboxylic acid). Crystal structural analysis reveals that compound 1 and 2 are 3D porous networks with open channels while compounds 3–5 are 2D MOFs. Complex 3 contains hydrogen bonded water molecules in between the 2D layers while 4 and 5 are highly dense compounds. The ligand L adopts different conformations which directed the final topology in these complexes. Complex 1–2 have a rare topology, gra, while 3–5 have four connected uninodal net with sql topology. The solvent accessible void volume for 1–3 comes out to be 51.2%, 52.3%, and 27% respectively. The gas adsorption studies reveal that 1–3 exhibit permanent porosity having type I isotherm and selectively adsorb CO2 gas over nitrogen and methane at low temperature with final uptake of 24.18 cc, 22.35 cc and 14.64 cc g−1 at STP, respectively. Vapour sorption study reveals that all the complexes selectively adsorb water vapour than methanol or ethanol vapours with final amount reached to 182.44 cc, 219.29 cc, 189.21 cc, 81.79 cc and 66.48 cc g−1 at room temperature. Solid‐state photoluminescence studies have been performed for all the complexes at room temperature (RT) and emission maximum for each complex are red shifted.