Silver/titanium dioxide (Ag/TiO2) nanoparticles, renowned as effective inorganic antibacterial agents with a wide spectrum of activity and minimal resistance induction, encounter challenges when incorporated into organic substrates. This integration often leads to particle aggregation, resulting in a substantial reduction in antibacterial efficacy. This study devised a novel approach involving loading Ag/TiO2 nanoparticles onto polyurea microcapsules (PUMC), forming hybrid-shelled microcapsules (Ag/TiO2-PUMC) using silane coupling agents. The preparation of polyurea microcapsules offers the advantages of rapid synthesis and mild reaction conditions, facilitating industrial-scale production. Additionally, loading Ag/TiO2 nanoparticles onto polyurea microcapsules helps alleviate the aggregation issue, and the organic nature of polyurea microcapsules enhances compatibility with organic substrates. Characterization techniques, including SEM, TEM, FTIR, XRD, UV–visible absorption spectroscopy, EPR and thermogravimetric analysis, were employed to confirm the successful grafting of Ag/TiO2 nanoparticles onto the PUMC. A comparative analysis between the two silane coupling agents, KH550 and KH792, revealed that the dual amino-functional silane coupling agent, KH792, played a pivotal role in chain extension during the microcapsule self-polymerization process. The antibacterial activity of the Ag/TiO2-PUMC was evaluated against Escherichia coli and Staphylococcus aureus. Remarkably, the hybrid-shelled microcapsules exhibited outstanding antibacterial efficacy, achieving a 99.99% antibacterial rate within just 0.5 hours. This performance surpassed unmodified Ag/TiO2 nanoparticles, highlighting the enhanced antibacterial efficacy of the hybrid-shelled microcapsule structure. This study presents a successful synthesis strategy for inorganic/organic hybrid-shelled antibacterial microcapsules and provides valuable insights for refining inorganic antibacterial agents. The demonstrated approach holds substantial promise for advancing the field of organic antibacterial materials.