The photophysical properties of a series of 9-arylacridinium conjugates in solid glass matrices composed of sucrose octaacetate have been determined. The fluorescence of the charge-shift states is significantly enhanced because of the retardation of nonradiative pathways for back-electron transfer. Changes of more than 3 orders of magnitude in back-electron-transfer rates (sucrose octaacetate glass vs conventional solvents at room temperature) were observed. Transient spectra displayed long-lived charge-shift species in the microsecond time regime for thianthrene acridinium conjugates. The rate retardation is associated with slow solvation times for surrounding solvent layers in the solid matrix. The red-edge effect (excitation wavelength-dependent fluorescence) for the arylacridinium ions in solid glass confirms the microheterogeneity of the sucrose octaacetate medium.