Several N-(2-halobenzyl)anilines and N-benzyl-2-haloanilines have been synthesized and their photochemical reactions studied. Upon irradiation, the aqueous acetonitrile solution of N-benzyl-2-chloroaniline was cyclized and reduced to give phenanthridine, 5,5',6,6'-tetrahydro-6,6'-biphenanthridyl (THBP), N-benzylaniline, and bibenzyl. Similar products were produced in the photochemical reactions of other halogenated N-benzylanilines, except iodo-substituted N-benzylanilines. No dimer (THBP) was produced from the iodo-substituted N-benzylanilines. Both singlet and triplet states are involved in the photochemical reactions of the haloarenes.