Synthesis of hierarchical macroporous structures has aroused great interest because of the potential applications and unique properties of the materials. In this research hierarchical macroporous polymer particles were fabricated by coassembly of polymersomes and polymer brushes on silica particles. In order to investigate the mechanism of the self-assembly and synthesize materials, two-component self-assembly of poly(2-(dimethylamino)ethyl methacrylate)-block-polystyrene (PDMAEMA55-b-PS316) and PS343, and three-component self-assembly of PDMAEMA55-b-PS316, PS343 and PS brushes on silica particles (SiO2-PS343) in THF/methanol mixtures were performed. In the coassembly of PDMAEMA55-b-PS316 and PS343, with an increase in PS343 content the morphology of the self-assembled structures changes from spherical micelles, to polymersomes, and to aggregated polymersomes. In the coassembly of PDMAEMA55-b-PS316, PS343 and SiO2-PS343, aggregated polymersomes and silica particles are formed. After etching silica particles with HF acid, macroporous polymer structures are produced. After quaternization of PDMAEMA blocks with methyl iodide, hierarchical macroporous structures with hydrophobic PS domains inside the structures are produced in aqueous solution. Toluene dispersed in aqueous phase is able to diffuse into the hydrophobic domains, and at high toluene content a transition from the hierarchical macroporous structures to hollow structures is observed.