The development of a new N-nitro type compound, dinitro-5,5-dimethylhydantoin (DNDMH), has been reported as an arene nitration reagent. The exploration demonstrated that arene nitration with DNDMH exhibited good tolerance with diverse functional groups. It is notable that, among the two N-nitro units of DNDMH, only the N-nitro unit on N1 was delivered to the nitroarene products. The N-nitro type compound with a single N-nitro unit on N2 cannot promote the arene nitration.