The acceptor-substituted anthracene N-(1-anthryl)-2,4,6-trimethylpyridinium shows dual fluorescence with a precursor-successor relationship which is most prominent in the intermediate temperature range. At 77 K, only the short-wavelength band (anthracene-type fluorescence originating formally from S 2 ) remains. The additional red-shifted fluorescence band observed at higher temperatures is of charge transfer type. A comparison of the radiative transition rates in absorption and emission suggests that structural relaxation leading to increased orbital overlap takes place in the excited state. This behaviour is unusual for a charge transfer state and is rationalized by the proposal of a bending motion (rehybridization of the nitrogen) induced by the increased electron density within the pyridinium ring.