Non-thermal plasma has been proved to be an effective and competitive technology for removing NO in flue gas since 1970. In this paper, the NO reduction mechanism of the non-thermal plasma reaction in NO/N2/O2 system was investigated using the method of spectral analysis and quantum chemistry. By the establishment of NO reduction and gas discharge plasma emission spectrum measuring system, the NO reduction results, gas discharge emission spectra of NO/N2/O2 and pure N2 were obtained, and then the model of molecular orbit of N2 either in ground state or its excited state was worked out using the method of molecular orbit Ab initio in Self-Consistent Field (SCF). It was found that NO reduction in NO/N2 gas discharge plasma was achieved mainly through a series of fast elementary reactions and the N(E6) at excited state was the base for NO reduction.