Triplet triplet energy transfer (EnT) is a fundamental activation pathway in photocatalysis. In this work, we report the mechanistic origins of the triplet excited state of carbazole-cyanobenzene donor-acceptor (D-A) fluorophores in EnT-based photocatalytic reactions and demonstrate the key factors that control the accessibility of the (LE)-L-3 (locally excited triplet state) and (CT)-C-3 (charge-transfer triplet state) via a combined photochemical and transient absorption spectroscopic study. We found that the energy order between (CT)-C-1 (charge transfer singlet state) and (LE)-L-3 dictates the accessibility of (LE)-L-3/(CT)-C-3 for EnT, which can be effectively engineered by varying solvent polarity and D-A character to depopulate (LE)-L-3 and facilitate EnT from the chemically more tunable (CT)-C-3 state for photosensitization. Following the above design principle, a new D-A fluorophore with strong D-A character and weak redox potential is identified, which exhibits high efficiency for Ni(II)-catalyzed cross coupling of carboxylic acids and aryl halides with a wide substrate scope and high selectivity. Our results not only provide key fundamental insight on the EnT mechanism of D-A fluorophores but also establish its wide utility in EnT-mediated photocatalytic reactions.