The photophysics of a series of Ru(II) dyads based on the 2-(1-pyrenyl)-1H-imidazo[4,5-f ][1,10]-phenanthroline ligand was investigated. The ability of these metal complexes to intercalate DNA and induce cell death upon photoactivation makes them attractive photosensitizers for a range of photobiological applications, including photodynamic therapy. In the present study, time-resolved transient absorption and emission spectroscopy were used to interrogate the photoinduced processes that follow metal-to-ligand charge transfer excitation of the complexes in solution. It was found that energy transfer to pyrene-localized intraligand triplet states, facilitated by torsional motion of the pyrene moiety relative to the imidazo[4,5-f ][1,10]phenanthroline ligand, was an important relaxation pathway governing the photophysical dynamics in this class of compounds. Biphasic decay kinetics were assigned to spontaneous (pre-equilibrium) and delayed emission, arising from an equilibrium established between 3MLCT and 3IL states. TDDFT calculations supported these interpretations.