We have identified a new (MC)-M-3 state bearing two elongated Ru-N bonds to the same ligand in [Ru(bpy)(3)](2+). This DFT-optimized structure is a local minimum on the (PES)-P-3. This distal MC state ((MCcis)-M-3) is destabilized by less than 2 kcal/mol with respect to the classical MC state ((MCtrans)-M-3), and energy barriers to populate (MCcis)-M-3 and (MCtrans)-M-3 from the (MLCT)-M-3 state are similar according to nudged elastic band minimum energy path calculations. Distortions in the classical (MCtrans)-M-3, that is, elongation of two Ru-N bonds toward two different bpy ligands, are not expected to favor the formation of ligand-loss photoproducts. On the contrary, the new (MCcis)-M-3 could be particularly relevant in the photodegradation of Ru(II) polypyridine complexes.