Hollow mesoporous polydopamine (HMPDA) microcapsules were prepared by a template method using silica nanoparticles as the templates. The template method was also used for the formation of mesoporous polydopamine (PDA), which is driven by π–π interactions of trimethylbenzene and PDA, in which the PDA wall with mesoporous structure can be obtained after template removal by extraction. Because of its surface mesoporous structure and large central cavity structure, HMPDA microcapsules have unique adsorption properties. Compared with other porous materials, PDA has better biosafety because dopamine itself is a bionic material. The above properties are of great significance for the application of HMPDA microcapsules in the field of biologic medicine, especially in drug carriers.