Abstract Absorption and fluorescence spectra, fluorescence quantum yields and decay times have been measured for new derivatives of 9-acetoxy-10-acetoxyhalogenophenylanthracene in dioxane. It is found that the strength of the absorption transition decreases with increases atomic number Z of the halogen substituent whereas the strength of the fluorescence transition is constant with the exception for the fluoro-substituted derivatives. The loss of mirror symmetry between the absorption and fluorescence spectra is more evident for the 10-(4-acetoxy-3'-halogenophenyl)anthracene derivatives than for the remaining compounds. The determined nonradiative electronic relaxation rate constant and "dark reactions" quantum yield increases with increasing Z value. These findings are explained on the basis of the spin-orbit coupling enlarged by the heavy substituent and through perturbation of the functional groups, which causes different changes of the molecular geometries in the S0 and S*1 states, respectively.