The electron transfer (ET) rates induced by the electronic excitation of different isomers of anthracene complexes with aniline derivatives are deduced from their fluorescence and fluorescence excitation spectra. The shapes of potential energy surfaces of locally excited and ionic surfaces are calculated with a special interest for the crossing areas of both surfaces. The dependence of the ET rates on the initial configuration is discussed and the assignments of calculated configurations to isomeric species (E and R isomers) are proposed.