The structural characterization of a hardly-isolatable molybdenum-dinitrogen complex bearing a PNP-type pincer ligand, which is assumed to be a key reactive complex in the stoichiometric transformation of a molybdenum triiodide complex [MoI3(PNP)] into the corresponding molybdenum nitride complex under an atmospheric pressure of dinitrogen, was carried out by using dispersive XAFS.