Aminobromination of α,β-unsaturated nitro compounds with benzyl carbamate and N-bromosuccinimide as nitrogen/bromine sources was reported. This new catalytic system tolerates a wide range of aromatic substrates, as well as heterocyclic and aliphatic substrates, resulting in good chemical yields. The reaction also proceeds smoothly with water as a medium in high efficiency. This practical aminobromination method was also proved to be suitable for large-scale preparation. Furthermore, the N-carbobenzoxy protecting group could be easily cleaved to afford the free vicinal haloamines.