Hydrophilic　magnetic　mesoporous　silica　microspheres　with　core-shell　structure　were　prepared　via　a　facile　approach　and　applied　as　an　enrichment　probe　for　low-abundance　glycopeptides　and　glycans　from　complex　biological　samples.　The　prepared　mesoporous　silica　microspheres　modified　with　gluconamide　groups　at　the　interior　surface　of　mesopore　channels　showed　more　prominent　features　with　respect　to　high　specific　surface　area　(490　m2/g),　narrow　pore　size　distribution　(2.5　nm),　and　high　saturation　magnetization　(23.87　emu/g),　endowing　them　with　hydrophilicity　and　size-exclusion　selectivity.　Taking　these　advantages　of　the　size-exclusion　and　the　hydrophilic　interactions,　the　hydrophilic　mesoporous　magnetic　microspheres　exhibited　specificity　for　glycopeptides　in　a　digest　of　horseradish　peroxidase.　The　detection　limit　for　horseradish　peroxidase　was　25　fmol.　In　addition,　the　hydrophilic　mesoporous　magnetic　microspheres　were　further　applied　to　the　selective　enrichment　of　N-linked　glycans　from　a　digest　of　human　serum.　The　successful　application　demonstrates　the　potential　of　the　hydrophilic　mesoporous　magnetic　microspheres　in　glycoproteomic　analysis.　©　2020,　©　2020　Taylor　&　Francis　Group,　LLC.