The resonance-enhanced multiphoton ionization (REMPI) of a mixed sandwich complex has been achieved for the first time when exciting (η7-C7H7)(η5-C5H5)Cr via the Rydberg 4pz state. The REMPI spectrum is indicative of unexpectedly small changes of the sandwich geometry on excitation. Time-dependent DFT calculations reveal fine effects of the ligand nature on the molecular and electronic structure variations accompanying electronic excitation. Different trends are predicted for the sandwich geometry transformations in the mixed sandwich complex and its symmetric isomer, (η6-C6H6)2Cr, both on Rydberg excitation and ionization.