Borondipyrromethene (BDP) naphthalenediimide (NDI) triads (BDP-NDI) and diiodo-BDP derivative (DiiodoBDP-NDI)) were synthesized to study the Förster resonance energy transfer (FRET) and its impact on the triplet state formation and dynamics. In these triads, diiodo-BDP and BDP are the energy donors and NDI is the energy acceptor. Nanosecond transient absorption spectra of triads indicated that triplet state is localized on NDI moiety, either by selective photoexcitation of the Diiodo-BDP or NDI unit. The intersystem crossing (ISC) is attributed to intramolecular heavy atom effect. The triplet state quantum yield was found to be 54% with a lifetime of 38 μs. However, no triplet state is observed for BDP-NDI system either by exciting BDP or NDI unit. Thus, we confirmed that charge recombination does not produce a triplet state. Interestingly, DiiodoBDP-NDI can be used as broadband excitable (500-620 nm) triplet photosensitizer, and high triplet-triplet annihilation (TTA) upconversion quantum yield of ΦUC = 2.8% was observed with 9,10-bis(phenylethynyl)-anthracene (BPEA) as a triplet acceptor/emitter.