The synthesis, structural characterization, electrochemistry, and molecular photophysics of [Ir(ppy)(2)(bpy-C[triple bond]C-Bodipy)](PF(6)), where ppy is 2-phenylpyridine and bpy-C[triple bond]C-Bodipy is 5-ethynyl-2,2'-bipyridine-8-phenyl-1,3,5,7-tetramethyl-4,4-bis(2,5-dioxaoct-7-ynyl)-4-bora-3a,4a-diaza-s-indacene (4), is presented. Static and dynamic photoluminescence and absorption measurements in conjunction with cyclic voltammetry were employed to elucidate the nature of the intramolecular energy transfer processes occurring in the excited state of the title chromophore. Parallel studies were performed on appropriate model chromophores (2 and 3) intended to represent the photophysics of the isolated molecular subunits, that is, triplet metal-to-ligand-charge-transfer ((3)MLCT) and triplet Bodipy intraligand ((3)IL) excited states, respectively. Upon charge transfer excitation of the title chromophore, the (3)MLCT based phosphorescence readily observed in 2 (Phi(em) = 0.027, tau = 243 ns) is quantitatively quenched resulting from production of the (3)Bodipy excited state through intramolecular triplet-triplet energy transfer. The formation of the (3)Bodipy-localized excited state is confirmed by features in the transient absorption difference spectrum, extended excited-state lifetime (tau = 25 micros), as well the observation of (3)IL Bodipy-based phosphorescence detected at 730 nm at 77 K. The low temperature Bodipy phosphorescence is readily produced in 4 as a result of the internal Ir(III) heavy atom.