Laser induced fluorescence (LIF) measurements of nitric oxide (NO) are performed in an atmospheric pressure microwave plasma jet, operated with a mixture of He and 3% air. The fluorescence signal of NO A 2Σ +(v = 0) is measured time and fluorescence wavelength resolved. Based on the evolution of the rotational spectrum at different positions in the plasma, we determined the thermalization time of the rotational distribution of NO A after pumping a single transition, at temperatures in the range 300-1500 K. Also, a LIF-RET (rotational energy transfer) model is developed to simulate the RET and to calculate the thermalization time. The RET rate coefficients are calculated using the energy corrected sudden-exponential power scaling law. It was found that it is necessary to take the fine structure of the rotational states into account. At room temperature the results of the measurement and the simulation are consistent, and the thermalization occurs during the laser pulse (11 ± 1 ns). At elevated temperatures the measurements show a large increase in thermalization time, up to 35 ± 4 ns at 1474 K. This time is much longer than the laser pulse, and of the order of the NO A lifetime. This means that for spectroscopy measurements of the rotational states of NO A, the RET has to be taken into account to derive gas temperatures from the rotational distribution of NO A.