Chemical synthesis of octasaccharide motif from Cranberry arabinoxyloglucan oligosaccharides with anti-adhesion activities has been achieved for the first time. Synthetic approach highlights the following features: 1) stereoselective constructions of 1,2-cis-Xyl bonds via the combination of reagent modulation and remote participation; 2) modular [1+3+1+3] orthogonal one-pot assembly of the target octasaccharide on the basis of glycosyl ortho-(1-phenylvinyl)benzoate, which avoids the issues such as aglycone transfer associated with one-pot glycosylation based on thioglycosides.