The ability to extract peptides and proteins from biological samples with excellent reusability, high adsorption capacity, and great selectivity is essential in scientific research and medical applications. Inspired by the advantages of coreshell materials, we fabricated a core-shell material using amino-functionalized silica as the core. Benzene-1,3,5-tricarbaldehyde and 3,5-diaminobenzoic acid were used as model organic ligands to construct a shell coating by alternately reacting the two monomers on the surface of silica microspheres. The resultant material featured an outstanding capability for the adsorption of cationic peptides, most likely owing to its porous structure, a large number of carboxylic functional groups, and low mass-transfer resistance. The maximum saturated adsorption capacity reached 833.3 mg/g and the adsorption process took only 20 min. Under optimized adsorption conditions, the core-shell material was used to selectively adsorb cationic peptides from the tryptic digestive solution of lysozyme and bovine serum albumin, Specifically, the analysis results showed seven cationic peptides in the eluate and twenty anionic peptides in the supernatant, which indicates the efficient trap of most cationic peptides in the digestive solution.