An arylnitrenium ion, N-methyl-N-(4-biphenylyl)nitrenium ion, was generated through photolysis of 1-(N-methyl-N-4-biphenylyl)amino-2,4,6-trimethylpyridinium tetrafluoroborate, and its reactions with various donor-substituted arenes (e.g., 1,3,5-trimethoxybenzene, mesitylene, 1,4-dimethoxybenzene, hexamethylbenzene, etc.) were examined using product analysis and laser flash photolysis. In general, trapping of the short-lived nitrenium ion by the arenes leads to three types of products: (1) the parent amine, N-methyl-N-4-biphenylylamine; (2) an ortho-adduct, where the ring position ortho to the nitrenium ion center is bonded to the arene ring; and (3) an N-adduct, where the nitrenium ion nitrogen is bonded to the trap. Laser flash photolysis studies show that the rates of these trapping reactions vary from 10(4) to 10(9) M-1 s(-1), depending on the structure of the arene trap. These trapping rate constants do not correlate with the one-electron oxidation potential of the arene, nor with the expected stability of a o-complex derived from direct electrophilic aromatic substitution. It is argued that the observed rate constants correspond to initial formation of a pi-complex between the arylnitrenium ion and the arene trap. This complex then forms the observed products.