By using an optical emission spectroscopic measurement method, the vibrational and rotational temperatures of nitrogen monoxide molecules are obtained for N2–O2 mixture microwave discharge plasma. We experimentally observed the γ-band (195–340 nm) spectrum of nitrogen monoxide. We also developed a method of theoretical calculation for its vibrational and rotational spectrum, with which we can fit the experimental results theoretically, so that the vibrational and rotational temperatures can be determined. Some experiments are carried out to examine relaxation process of excited states of the N2–O2 gas mixture plasma together with its N2 ratio dependence. We discussed the dominant molecular processes and excitation kinetics for the formation of NO A 2Σ+ state under different discharge conditions, particularly on the N2–O2 mixture ratio.