By using an optical emission spectroscopy measurement method, the vibrational and rotational temperatures of nitric oxide molecule in N2-O2 microwave discharge are obtained. We detect the radiation lies in γ-band (195 – 340nm) of nitric oxide, which comes from the A 2Σ+ to X 2Π electronic transition. We also developed a theoretical calculation for the vibration and rotation spectrum, with which we can fit the experimental results theoretically, so that the vibrational and rotational temperature can be determined. We also carried out some experiments to examine the cooling process and N2 ratio dependence, according to which we discussed the molecular combination and excitation reactions under different plasma conditions.