Two new formamidinate-bridged Rh 2 II,II complexes, cis-[Rh 2 II,II (µ-DTolF) 2 (µ-np) 2 ] 2+ (3; DTolF = N,N′-dip -tolylformamidinate; np = 1,8-naphthyridine) and cis-[Rh 2 II,II (µ-DTolF) 2 (κ 2-dap) 2 ] 2+ (4; dap = 1,12-diazaperylene), were synthesized from [Rh 2 II,II (µ-DTolF) 2 (CH 3 CN) 6 ](BF 4) 2 (1), and their properties were compared to those of [Rh 2 II,II (µ-DTolF) 2 (phen) 2 ](BF 4) 2 (2). Density functional theory (DFT) and electrochemical analyses support the description of the highest occupied molecular orbitals (HOMOs) of 3 and 4 as possessing contributions from the metals and formamidinate bridging ligands, with Rh 2 /form character, and lowest unoccupied molecular orbitals (LUMOs) localized on the respective diimine ligand np and dap π* orbitals. Both 3 and 4 display strong, low energy Rh 2 /formdiimine(π*) metal/ligand-to-ligand charger transfer (1 ML-LCT) transitions with maxima at 566 nm (ε = 3,600 M −1 cm −1) for 3 and at 630 nm (ε = 2,900 M −1 cm −1) for 4 in CH 3 CN. Time dependent-DFT (TD-DFT) calculations support these assignments. The ability of both the bridging np and chelating dap diimine ligands to produce strong absorption of these Rh 2 II,II complexes throughout the visible region is potentially useful for the development of new photocatalysts for H 2 production and photochemotherapeutics.