The synthesis and characterization of one symmetrical bis-1-substituted-1H-tetrazole (69%) via a Huisgen-type 1,3-dipolar cycloaddition, as well as, one symmetrical aza-linked bis-5-substituted-1H-tetrazole (64%) via a classic Huisgen 1,3-dipolar cycloaddition followed by a reductive aza-coupling under mild reaction conditions are described. The main reason behind these tetrazole-based ligands is to construct novel Metal-Organic Framework (MOF) architectures to evaluate its CO2 capture properties under relative humidity conditions. It is worthy to note that both herein reported products have not been synthesized nor isolated, anywhere. Besides, the synthesis of new ligands to fabricate novel MOFs with potential application in environmental remediation has become in a high valued field of opportunity for synthetic chemists and materials engineers.