It is becoming increasingly clear that the presence of a fucose moiety attached to the acetylglucosamine unit (GlcNAc) of N-glycans is important the in vivo activity of erythropoietin. However, the synthesis of N-glycans, especially fucose-containing hybrid type N-glycans, is very difficult due to the risk of breaking the α-glycosidic bond in the Fucα(1-6)GlcNAc unit during the tedious process of protection-deprotection. In this paper, the key point is that a benzyl group was used as a sterically demanding protecting group, which led to the regio-and stereoselective construction of Fucα(1-6)GlcNTroc disaccharide due to the “steric hindrance effect” and “armed activation” of the benzyl group when glycosylating allyl 3-benzyl-2-deoxy-2- (2,2,2trichloroethoxycarbonylamino)-α-D-glucopyranoside (compound 3) with methyl 2-O-Benzyl-3,4-di-O-acetyl-1-thio-β-L-fucopyranoside (compound 2) in dichloromethane and cyclopentyl methyl ether (CPME) in the presence of the methyl triflate (MeOTf) and 2,6-di-tert-butyl-4-methylpyridine (DTBMP). The selective formation of Fucα(1-6)GlcNAc disaccharide unit (compound 1) simplifies the synthetic route. The compound 1 was characterized by 1H nuclear magnetic resonance spectroscopy and mass spectrometry. This work provides the basis for further study of the solid-phase synthesis of fucosecontaining N-glycans.