Glycosylation of 4-aminostyrene with alpha-D-glucopyranose, alpha,beta-D-mannopyranose, L-rhamnopyranose, and alpha,beta-L-arabopyranose in alcoholic medium has been studied. 4-Aminostyrene N-glycosides like 1-(4-vinylphenyl)amino-1-deoxy-D-glucopyranose, 1-(4-vinylphenyl)amino-1-deoxy-beta-D-mannopyranose, 1-(4-vinylphenyl) amino-1-deoxy-beta-L-rhamnopyranose, and 1-(4-vinylphenyl)amino-1-deoxy-L-arabopyranose were synthesized and characterized for the first time.