Electrogenerated chemiluminescence, or electrochemiluminescence (ECL), is nowadays a powerful transduction method in electroanalysis, in particular regarding the application in clinical diagnostics. Indeed, its superior capability relies in the fruitful combination of electrochemical and photoluminescence properties. The research on efficient ECL luminophores has brought a wide range of molecules, form organic systems to inorganic complexes, however, despite this large pool of luminophores available, tris(2,2′-bipyridine)ruthenium (II) [Ru(bpy)3]2+ is still leading since the first report in 1972, in both academic research and commercially available systems. To acknowledge the outmost importance of this inorganic complex, here we report the photophysical and electrochemical properties of [Ru(bpy)3]2+ and its derivatives obtained by ligand design for application in ECL.