A theoretical analysis, based on density functional theory, has been carried out to study photoinduced processes within a recently experimentally characterized (Laine, P. P.; Bedioui, F.; Loiseau, F.; Chiorboli, C.; Campagna, S. J. Am. Chem. Soc. 2006, http://dx.doi.org/10.1021/ja058357w.) series of Os(II) bis-tpy complexes (tpy = 2,2': 6'2"-terpyridine) functionalized by 2,4,6-triarylpyridinium groups, TP+. These dyad systems, designed to produce a charge-separated state (CSS) upon light excitation, are made up of a photosensitizer unit ( P, the metal complex) and a tunable acceptor unit (A, the TP+). A full ab initio characterization of the electronic and structural properties of the lowest-lying triplet excited states, as well as of the CSS, allowed for a complete rationalization of the photoinduced processes taking place within the dyads. Among salient insights, theory allowed (i) substantiation of the inner P structural planarization as the relaxation mode of the MLCT states, (ii) confirmation of the existence of a ligand-centered triplet excited state ((LC)-L-3) shown to essentially involve the nitro substituent of A (TP+-NO2) and lying very close in energy to the P-centered (MLCT)-M-3 state, and (iii) a demonstration that the energy of the (LC)-L-3 level is independent of intercomponent tilt angle (theta(1)). On this basis, the occurrence of a reversible electronic energy transfer between the (MLCT)-M-3 and the (LC)-L-3 states could be substantiated and shown to depend on the intramolecular conformation represented by theta(1), which actually governs their electronic coupling (essentially via the degree of intercomponent conjugation). These computational issues were checked against experimental data already available and the results of a specifically undertaken photophysical study. Finally, CSS formation has been confirmed by studying the spin density patterns of reduced nitro-derivatized dyads. Taken together, these findings accurately account for the different excited-state behaviors of the dyads as a function of the level of structural restriction of their intercomponent conformation (and related amplitude for torsional fluctuations), thus providing theoretical evidence of conformationally gated photoinduced electron-and energy-transfer processes.