The photon-excited NO2 at 308 nm has been investigated by Tha-Resolved FTIR spectroscopy. The IR fluorescence from highly excited NO2(X2 A1) in u1 vibrational mode has been observed. These excited states are resulted from the strong vibronic mix ing of electronic excited A2 B2/B2 B1 states with the grou-nd X2 A1 state. It is considered that symmetric stretching v1 mode is reserved from the photolysis because its vibrational style is unsuitable for dissociation.