The self‐assembly of the two zinc(II) metal–organic frameworks, [Zn2(L)(bdc)2]·3MeOH·4H2O}n (1, L = 2‐(pyridin‐4‐yl)‐3H‐imidazo[4,5‐c]pyridine, H2bdc = 1,4‐benzenedicarboxylic acid) and [Zn2(L)(bdc)2]·2DMF·H2O}n (2), was achieved under mild reaction conditions. Both compounds 1 and 2 were structurally characterized by single‐crystal X‐ray diffraction analysis. Interestingly, the coordination modes of the ligand L in two structures are entirely different. Compounds 1 and 2 were made up of paddle wheel‐shaped {Zn2(O2C)4} secondary building unit (SBU) clusters, which adopted three‐dimensional structures with a pcu topology. Rich weak interactions were observed in the structures of both 1 and 2. The uncoordinated imidazole and pyridine moieties exhibited electron donor–acceptor interactions, π–π stacking, hydrogen bonding, and CH–π interactions. These interactions also facilitated the abilities of the framework to adsorb CO2 molecules. Gas adsorption studies revealed that compound 1 selectively adsorbed CO2 (131.1 cm3/g) over N2 (23.5 cm3/g) and H2 (36.5 cm3/g) at a pressure of 1 atm.