A total synthesis of tumor-associated glycolipid antigen sialyl Lea, and a first total synthesis of glycononaosyl ceramide with a dimeric Leasequence are described. Regio-and stereoselective coupling of sialyl donor12with suitably protected Leatrisaccharide fluoride17was performed by orthogonal glycosylation to give the expected tetrasaccharide18in good yield. Glycosylation of its acetate19with lactose derivative8by use of Cp2HfCl2-AgOTf as a promoter, gave the desired hexasaccharide20. On the other hand, glycosylation between sialyl Leatetrasacchande donor34and Leapentasaccharide acceptor35under the agency of PhSeOTf afforded the desired nonasaccharide36. After replacement of the benzyl groups in20and36by acetyl groups, the anomeric acetate was transformed into the α-trichloroacetoimidates23, 39and the fluoride derivative40. The crucial couplings of23, 39and40with azidosphingosine derivative3or ceramide derivative4were executed to afford β-glycosides24and41. Compound24was converted to26viareduction of the azide group followed byN-acylation. The target gangliosides1and2were obtained from26and41, respectively, by selective cleavage of the methyl ester, conversion of theN-phthalimido group to theN-acetamido group, andO-deprotection.