An efficient and eco-friendly protocol for the chemoselective N-benzyloxycarbonylation of amines was described.The reaction of amines with benzyl chloroformate (Cbz-Cl) in the presence of PEG-600 at room temperature afforded the corresponding N-Cbz derivatives in excellent yields.The method is applicable to the N-Cbz protection of aliphatic (acyclic and cyclic) and aromatic amines.