Resonance Raman and electronic absorption spectra have been measured for the ozonide ion, O−3, produced in single crystals of KClO3 and NaClO3 by irradiation with γ rays. The O−3 ions are oriented in four to six symmetrically nonequivalent positions in KClO3 and appear to be oriented in two nonequivalent positions in NaClO3. Differences between the nonequivalent orientations affect both the ground and excited electronic states of O−3 as well as its ground vibrational states. The progressions of ν1 observed in the electronic spectra show that the vibrational spacing of ν1 in the excited electronic state is about 857 cm−1 as compared with the ground state spacing of about 1020 cm−1. Measurements of relative Raman intensities obtained with different exciting lines indicates that excitation near the center of a vibronic transition (0–n′) produces extra enhancement of the intensity of the nν1 vibrational transition.