The optical-optical double resonance time of flight (OODR-TOF) spectroscopy technique was employed to examine the 65 000-66 500 cm(-1) region of the nitric oxide spectrum. In this region, we detected the following three electronic states: E (2)Sigma(+) (v = 2) (Rydberg, state), B (2)Pi (v = 23) (valence state), and L (2)Pi (v = 4) (valence state). The rotational structure analysis of an unexpected band in the red part of the spectra revealed the presence of a new super-excited (2)Sigma(+) Rydberg state at similar to 13.3 eV, which was populated through a three-photon transition from the intermediate A (2)Sigma(+) (v = 0) state. This super-excited statei converges to the NO (a(3)Sigma(+)) ionic state with electronic configuration (1 sigma)(2)(2 sigma)(2)(3 sigma)(2)(4 sigma)(2)(5 sigma)(2)(1 pi)(3)(2 pi)(1)(3s sigma)(1).