Glycoprotein is involved in a variety of biological activities and has been linked to a number of diseases. Glycopeptide enrichment prior to mass spectrometry (MS) detection is crucial to reduce interference, improve detection efficiency, and analyze proteomics deeply and comprehensively. Here, we prepared a novel magnetic hydrophilic material combining tannic acid (TA) and L-cysteine (L-Cys) through a simple and fast procedure. Owing to the synergistic hydrophilic interaction of TA and L-Cys, the obtained adsorbent material shows excellent enrichment performance toward N-glycopeptides with low detection limit, high selectivity, and good reusability. Besides, the material can also be utilized for the enrichment of N-glycopeptides in human serum and saliva, which shows its application prospect in complex biological samples.