The first total synthesis of a major component of marine glycolipid vesparioside B (Scheme 1, 1, R-1 = n-C22H45) R-2 = n-C14H29) has been accomplished through a convergent [4 + 3] coupling strategy. Key steps included stereoselective installment of a set of challenging 1,2-cis-glycoside bonds. A 2-quinolinecarbonyl-assisted alpha-galactosylation and a novel beta-arabinosylation were developed, respectively, to synthesize the alpha-galactofuranosidic and the beta-arabinopyranosidic linkages. Furthermore, a 4,6-O-benzylidene-controlled alpha-galactopyranosylation reaction allowed the efficient connection of the left tetrasaccharide donor 2 with the right disaccharide lipid acceptor 3, hence leading to the total synthesis of 1.