In order to explore the antimicrobic materials, new strategies for synthesis of particles were paid more and more attention as it was crucial to the advancement of material technology and environmental. In this work, we provided a strategy for construction of novel hollow-carved microspheres (HCMs) by a simple method of emulsion interfacial polymerization (EIP). Firstly, using sodium p-styrene sulfonate (SSS) and styrene (St) as hydrophilic/hydrophobic and rigid comonomers, diallyl dimethylammonium chloride (DMA) as cationic cross-linking monomer, azobisisobutyronitrile (AIBN) as initiator, hexane as a pore-forming agent, the HCMs were synthesized by EIP. Then, the quaternized HCMs (QHCMs) was prepared by quaternization of hydrophilic sodium sulfonate groups ( SO 3 Na). The composition and micromorphology of the obtained microspheres were characterized by FT-IR, XPS, EDS, DLS, SEM, and TEM. The antibacterial properties of QHCMs were tested against Escherichia coli and Staphylococcus aureus. At a concentration of 320 μg/ml QHCMs, the bacteriostatic activities of S. aureus and E. coli decreased by more than 91.7% and 86.4%, respectively, which was confirmed by the colony forming units and regeneration curves. In summary, a novel antibacterial polymer material was successfully synthesized by EIP and quaternization, which could be widely used in coating materials to reduce bacterial infection.