Polymeric particles with diverse surface and internal hierarchical nanostructures were prepared by the dynamic self-assembly of a fluorine-containing diblock copolymer, poly(tert-butylacrylate)-b-poly(2-[(perfluorononenyl) oxy] ethyl methacrylate) (PtBA-b-PFNEMA) in THF/water mixtures. The surface patterns and internal structures both originated from the microphase separation of PtBA-b-PFNEMA and could be tuned by the preparation conditions. Besides, the interface limitations and geometric confinement of the particles' morphology resulted in the formation of different phase separation structures on the surface and inside the particles. By tuning the water content and preparation temperature, almost parallel cylindrical domains, twisted interconnected cylindrical domains, or spherical domains were obtained on the surface of the particles. Meanwhile, the internal structures of the particles transformed from inner stacked lamella with outer onion-like structures, inner disordered with outer onion-like structures, to bicontinuous structures as the chain mobility and incompatibility of the two blocks could be controlled by the preparation condition. Therefore, the integration of diverse cylindrical surface structures and bicontinuous or onion-like inner structures into hierarchical nanoparticles was achieved.