Trivalent glycoconjugates, each bearing a biotin side arm in addition to three different sugar ligands, have been synthesized on a solid support. The conjugates were assembled on an orthogonally protected pentaerythrityl tetramine core that was anchored to the support through a backbone amide linker. Peptide coupling chemistry was applied to elongate three of the branches with β‐alanine and a fully acylated glycosylacetic acid. The fourth branch was levulinoylated and oximated with aminooxy‐derivatized D‐biotin, followed by acidolytic release into solution. The acyl protecting groups were removed by methoxide‐catalyzed transesterification in methanol.