Biocompatible C-8-functionalized magnetic carbonaceous polysaccharide microspheres are synthesized via a facile, low-cost, and large-scale route, and their use for the enrichment of peptides from protein digest mixtures is presented. The process of enrichment is very simple, quick, and efficient. Peptides loaded onto the C-8-functionalized magnetic carbonaceous polysaccharide microspheres can be directly analyzed by MALDI-TOF-MS without prior elution from the microspheres.