Catalytic distillation (CD) technology was used in the direct amination of benzene to aniline with aqueous ammonia and hydrogen peroxide over a V-Ni/Al2O3 catalyst. The effects of several parameters (including the packing manners of the catalytic column, the feed ratio, the distillation temperature, and the reaction time) on the amination were studied. It was found that the yield of aniline was significantly improved in the CD process, in comparison to the kettle-type reaction.