Three systematically functionalized 6-azolyl-2,2′-bipyridine ligands were prepared from reactions initiated by 6-cyano-2,2′-bipyridine. These ligands readily reacted with the metal alkyl reagents GaMe 3 and InMe 3 to afford the pentacoordinate complexes [(fpzbpy)MMe 2 ] (1a, M) Ga; 1b, M) In), [(ftzbpy)MMe 2 ] (2a, M) Ga; 2b, M) In), and [(N4bpy)MMe 2 ] (3a, M) Ga; 3b, M) In), in which (fpzbpy)H, (ftzbpy)H, and (N4bpy)H denote 6-pyrazolyl-, 6-triazolyl-, and 6-tetrazolyl-substituted 2,2′-bipyridine, respectively. These complexes exhibited moderate blue-green emission ranging from 412 to 493 nm. On the other hand, treatment of the bidentate 2-pyridyl tetrazole ligand (pyN4)H with InMe 3 afforded the bridged dimer [Me 2 In(pyN4)] 2 (4). Calculation based on time-dependent density function theory (TDDFT) showed that the S 1 state of complexes 1-3 is mainly attributed to an allowed intraligand π f π* electronic transition located at tridentate chelating moieties, together with a small contribution (<10%) of gallium (or indium) f π* (ligand) charge transfer transition. Accordingly, the corresponding emission properties of 1a-3a (or 1b-3b) can be rationalized using the correlation between the substituent effect of azolyl groups and the relative HOMO/LUMO energy level.