The synthesis, photophysics, and electrochemiluminescence (ECL) of four water-soluble dinuclear Ir(III) and Ru(II) complexes (1-4) terminally-capped by 4'-phenyl-2,2':6',2''-terpyridine (tpy) or 1,3-di(pyrid-2-yl)-4,6-dimethylbenzene (N^C^N) ligands and linked by a 2,7-bis(2,2':6',2''-terpyridyl)fluorene with oligoether chains on C9 are reported. The impact of the tpy or N^C^N ligands and metal centers on the photophysical properties of 1-4 was assessed by spectroscopic methods including UV-vis absorption, emission, and transient absorption, and by time-dependent density functional theory (TDDFT) calculations. These complexes exhibited distinct singlet and triplet excited-state properties upon variation of the terminal-capping terdentate ligands and the metal centers. The ECL properties of complexes 1-3 with better water solubility were investigated in neutral phosphate buffer solutions (PBS) by adding tripropylamine (TPA) as a co-reactant, and the observed ECL intensity followed the descending order of 3 > 1 > 2. Complex 3 bearing the [Ru(tpy)2]2+ units displayed more pronounced ECL signals, giving its analogues great potential for further ECL study.