The Rh(NN)$+-w+ dyad, which contains a Rh(II1) polypyridine moiety (Rh(NN)f+) and a N,N'-bridged diquatemarized 4,4'dimethyl-2,2'-bipyridine (p) as covalently linked components, has been synthesized and used in the study of intramolecular electron transfer. The study, performed by laser flash photolysis, makes use of a relatively unconventional reaction scheme. First, bimolecular electron-transfer quenching of the Rh(NN)t+-localized excited state of the dyad (using 1,2,3-trimethoxybenzene as external reductant) is used to generate the reduced dyad in the thermodynamically unfavored Rh(NN),"-w+ form. Then, this species is observed to relax by a fast (k = (3 f 1) X 10's-I) intercomponent charge-shift process to the stable (AGO, ca. 0.2 eV) Rh(NN)?+-DQ+ form. A slower bimolecular back-electron-transfer reaction with the radical cation of the external quencher (k = 3.3 X lo9 M-I s-l) finally brings back the dyad to its original oxidation state.