This report presents the photochemistry and photophysics of the series of dimeric complexes fac-(b)ReI(CO)3-[CpMII(arene)]2+, where b = a series of substituted 2,2’-bipyridine ligands, Cp = eta5-cyclopentadienyl, and M = Fe and Ru. The two metals are linked by 4-benzylpyridine, which is coordinated eta1 to Re(I) via the pyridyl nitrogen and eta6 to M(II) via the benzyl group. Near-UV photoexcitation of these complexes produces the luminescent dpi (Re) --> pi* (diimine) metal-to-ligand charge-transfer (MLCT) state. The MLCT state is quenched by intramolecular exchange energy transfer (E(N)T) to the reactive 3d-d state of CpM(arene). Evidence that E(N)T occurs is provided by the observation of the following reaction during Re --> diimine MLCT photoexcitation : (b)ReI(CO)3-[CPMII(arene)]2+ --> hv, CH3CN (b)ReI(CO)3(4-benzylpyridine)+ + CpM(CH3CN)3+. The driving force for Re --> M E(N)T (DELTAE(E(N)T)) is varied by changing the energy of the Re --> diimine MLCT state and by varying M. For M = Ru, E(N)T is weakly endothermic, and for M = Fe, E(N)T is moderately exothermic. The rate of intramolecular E(N)T is estimated from the quantum efficiency for CpM(arene) loss from the dimers and From MLCT emission lifetimes. The activation energy and frequency factor for E(N)T in the (b)Re-Ru series is determined from the temperature dependence of the MLCT emission decay rate.