The reaction of acenaphthene with nitrobenzene was investigated in the presence of AlCl 3 . The results showed that the reaction proceeded via carboncation-electrophilic substitution reaction and free radical substitution reaction pathway. The products of acenaphthenyl phenylamine and biacenaphthyl could be synthesized by this reaction. The influence of the amount of AlCl 3 and the temperature on the components of products were also studied in this reaction. The reaction of acenaphthene with nitrobenzene was investigated in the presence of AlCl 3. The results showed that the reaction proceeded via carboncation-electrophilic substitution reaction and free radical substitution reaction pathway. The products of acenaphthenyl phenylamine and biacenaphthyl could be synthesized by this reaction. The influence of the amount of AlCl 3 and the temperature on the components of products were also studied in this reaction.