The intramolecular exciplex formation and photodissociation in a supersonic free jet have been studied for deuterated anthryl bichromophoric EDA systems 1-(9-anthryl-d(8))-3-(m-(N,N-dimethylamino)phenyl)propanes (9-An-d-m-DMA) in comparison with the corresponding undeuterated compounds (9-An-m-DMA). Fluorescence hole burning depletion spectra in the anthryl deuterated 9-An-d-m-DMA suggests the presence of two distinct isomeric conformers. The S-1 vibrational energy thresholds for the exciplex formation in the two isomeric forms of the deuterated compounds are considerably smaller than those of the respective undeuterated compounds. The photodissociation of the exciplex leading to the formation of the excited-state anthryl moiety was observed in the excitation of the transient absorption band of the jet-cooled exciplex (S-n-S-1). The decay time of the photodissociation-induced anthryl fluorescence is shorter for 9-An-d-m-DMA than for 9-An-d-m-DMA These deuteration effects of the anthryl moiety on the formation and photodissociation of the exciplex may be attributed to the role of the vibrational level density of the anthryl moiety in these excited-state reaction dynamics. The shorter decay time of the photodissociation-induced anthryl fluorescence of 9-An-d-m-DMA relative to 9-An-m-DMA is consistent with the conclusion that the emission originates from the vibrationally highly excited S-1 anthryl moiety.