A series of binuclear Ru(II)-Rh(III) complexes of general formula (ttpy)Ru-tpy-(ph)(n)-tpy-Rh(ttpy)(5+) (n = 0-2) have been synthesized, where ttpy = 4'-p-tolyl-2,2':6,2"-terpyridine and tpy-(ph)(n)-tpy represents a bridging ligand where two 2,2':6',2"-terpyridine units are either directly linked together (n = 0) or connected through one (n = 1) or two (n = 2) phenyl spacers in the 4'-position. This series of complexes is characterized by (i) rigid bridge structures and (ii) variable metal-metal distances (11 Å for n = 0, 15.5 Å for n = 1, 20 Å for n = 2). The photophysics of these binuclear complexes has been investigated in 4:1 methanol/ethanol at 77 K (rigid glass) and 150 K (fluid solution) and compared with that of mononuclear [Ru(ttpy)(2)(2+) and Rh(ttpy)(2)(3+)] or binuclear [(ttpy)Ru-tpy-tpy-Ru(ttpy)(4+)] model compounds. At 77 K, no quenching of the Ru(II)-based excited state is observed, whereas energy transfer from excited Rh(III) to Ru(II) is observed for all complexes. At 150 K, energy transfer from excited Rh(III) to Ru(II) is again observed for all complexes, while quenching of excited Ru(II) by electron transfer to Rh(III) is observed, but only in the complex with n = 0. The reasons for the observed behavior can be qualitatively understood in terms of standard electron and energy transfer theory. The different behavior between n = 0 and n = 1, 2 can be rationalized in terms of better electronic factors and smaller reorganizational energies for the former species. The freezing of electron transfer quenching but not of energy transfer, in rigid glasses reflects the different reorganizational energies involved in the two processes. Unusual results arising from multiphotonic and conformational effects have also been observed with these systems.