The concentration of nitrogen oxides (NO2, NO, N2O, etc.) in power plant is an important index of environmental protection. Aiming at the problem that the detection accuracy of nitrogen oxides concentration based on spectral analysis could be interfered by all kinds of factors, such as temperature, moisture content, tar, naphthalene, noise of electric devices, optical lens aging, interference at spectral absorption characteristics of polluting gases etc, it is difficult to improve in a single way. At first, the hardware modification is favorable for gas purification and filter. And then, the selflearning and selftraining ability of RBF neural network can save the traditional model for the study of interference factors, and make the data processing more efficient. On the basis of a large thermal power plant’s real data in 2015, the computer simulation and analysis show that this method can improve the accuracy effectively. The overallaverage deviation is 0.841%.