Excited-state charge transfer interaction was studied in bichromophoric electron donor-acceptor (EDA) systems, 1- and 9-(p-N,N-(dimethylamino)phenylethyloxy)anthracenes (1- and 9-An-O(CH2)(2)-DMA) and 1- and 9-(p-N,N-(dimethylamino)benzyloxy)methylanthracenes (1- and 9-An-CH2OCH2-DMA), in supersonic expansion. Intramolecular exciplex fluorescence, depending on excess vibrational energy, was observed in jet-cooled 9-An-O(CH2)(2)-DMA. In 1-An-O-(CH2)(2)-DMA, the existence of two isomeric conformers was observed in fluorescence excitation, spectra, The UV fluorescence excitation spectrum shows well-resolved vibrational structures, while the visible fluorescence excitation spectrum exhibits considerably broad and 4.5 nm blue-shifted vibrational structures from the UV excitation spectrum. The latter visible excitation spectrum is attributable to intramolecular van der Waals interaction between EDA moieties followed by the exciplex formation. Another conformer exhibits no significant exciplex fluorescence. The other ethereal compounds, 1- and 9-An-CH2OCH2-DMA, exhibit neither exciplex nor charge-transfer complex fluorescence in supersonic expansion but show exciplex fluorescence in solution.