Glycosylation is one of the most important post translational modifications of proteins and aberrant glycoprotein expression has been associated with various diseases including cancer.Enrichment of N-linked glycopeptides has been significantly important because they are crucial to further structural determination and functional elucidation of N-linked glycoprotein.Herein,by combining the synergistic effect of polyvalent interaction from polymer brush and specific recognition of PBA and saccharide residues,we designed PBA polymer brush modified silica microsphere materials (PBA-PB@SiO2).The as-prepared PBA-PB@SiO2 demonstrated higher enrichment efficiency and selectivity than both monolayer PBA@SiO2 and commercial PBA-agarose.The feature might be attributed to: 1) 3D contact between polymer brushes on PB-PBA@SiO2 and glycopeptides provides a polyvalent interaction mode; 2) high wettability under high ACN concentration and high pH condition suppresses the non-specific binding of non-glycopeptides and enhances retention of glycopeptides.Moreover,the polyvalent interaction mode greatly improves the enrichment capacity for glycopeptides.We believe that this new kind of glycopeptides targeting material may be a useful tool for glycoproteome.