Several (3 + 2) cycloaddition reactions catalyzed by dirhodium(II) complexes between N-arylaminocyclopropane and alkenes derivative have been developed. Preliminary mechanism studies suggest that dirhodium(II) complexes may decrease the bond-dissociation energy (BDE) of the N–H bond of N-arylaminocyclopropanes for N–H bond activation, thus facilitating the formation of N-centered radicals by loss of a hydrogen radical.