In recent years, core–shell composite particles with organic polymer as the core and inorganic SiO₂ as the shell have attracted widespread attention and prompted robust scientific endeavors. The encapsulation of SiO₂ can endow the polymer core with a variety of important properties, and is of great significance for the synthesis of multi–functional materials, having favorable application prospects in coating, polishing, medical, optical, magnetic, lubrication and other fields. In this paper, the recent advances in the preparation of core–shell polymer@SiO₂ composite particles are reviewed. From the perspective of interface bonding mechanisms between the core and the shell, this paper mainly focused on the following five aspects: Pickering stabilization, acid–base interaction, charge interaction, bridging of coupling agent, hydrogen bonding, and other actions. Additionally, applications of core–shell polymer@SiO₂ particles are also discussed. It is expected that this article can provide scientific guidance for the preparation of polymer@SiO₂ core–shell particles, further enriching their species and broadening their applications.