It has been proved by ab initio calculation and theoretical analysis that there exist [N2]2--N2 molecular dimers with D2h symmetry group, and there also exists an electric dipole excimer-like transition a1B2g→a1B3u. The theoretical spectra accord with the experimental results for transition a1B2g→a1B3u. The stimulated emission characteristic of N2 molecular dimer was researched through the microwave excited highly pure nitrogen and the method of amplified spontaneous emission. The experimental results show that N2 molecular dimer has stimulated emission characteristics when the microwave power is more than 100 W and the N2 pressure is in the range from 260 Pa to 2200 Pa.