We use a spectroscopic method to diagnose the microwave discharge plasma of N2–O2 mixtures. We succeed in observing NO δ-band radiation peaks when the oxygen partial pressure is smaller than 3%. In order to quantitatively investigate the de-excitation processes of the NO C 2Π excited state, we improve our self-consistent kinetic model to include some of the main excited states of NO molecules. In providing our numerical results, we discuss a reasonable NO C 2Π de-population process by that involves collision with the O2 X 3Σg− state molecule, which leads to the disappearance of δ-band radiation. We propose an indirect proof that this de-population process results in an increase in the vibrational temperature of NO A 2Σ+.