A hydrophilic interaction chromatography (HILIC) strategy is considered as an efficient strategy for efficient glycopeptide enrichment. Here, a novel hydrophilic material (denoted as magCDP@Ada-MSA) was constructed through host–guest interaction between crosslinked β-cyclodextrin (β-CD) polymers and mercaptosuccinic acid (MSA) derived adamantane. On the one hand, crosslinked β-CD polymers have great hydrophilicity due to their abundant hydrophilic hydroxyl groups. On the other hand, the hydrophilic functional molecule MSA was introduced into crosslinked β-CD polymers through host–guest interaction for further hydrophilic modification of the material. Hydroxyl groups in crosslinked β-CD polymers and carboxyl groups in MSA together endow the material with excellent hydrophilicity and good affinity toward glycopeptides. The prepared hydrophilic material demonstrated rapid magnetic separation (within 5 s) and reusability (at least 10 cycles). Thanks to the above advantages, magCDP@Ada-MSA showed satisfactory performance for the specific enrichment of glycopeptides (selectivity, 1 : 500 molar ratios of HRP/BSA and sensitivity, 0.1 fmol μL⁻¹). Moreover, magCDP@Ada-MSA was successfully applied for selective glycopeptide enrichment from complex biological samples (human serum and saliva).