A facile, efficient and substrate-selective oxidation of the primary amines with NaClO as oxidant catalyzed by β-cyclodextrin (β-CD) has been developed in water for the first time, and the behavior of β-cyclodextrin that catalyzed the primary amines to nitriles in water was investigated. It was found that the primary amines which could form host-guest complexes with β-cyclodextrin were oxidized to nitriles with excellent yields at ambient temperature. The results show that β-cyclodextrin worked not only as a solubilizing agent but also as a catalyst in these reactions.