Silica nanoparticle vesicles (NPVs) with encapsulating capability and surface permeability are highly attractive in nanocatalysis, biosensing, and drug delivery systems. Herein, we report the facile fabrication of silica NPVs composed of a monolayer of silica nanospheres (SNSs, ca. 15 nm in diameter) through the block copolymer-mediated self-assembly of SNSs. The silica NPVs gain different surface topographies, such as raspberry- and brain coral-like topographies, under controlled heat treatment conditions. The vesicular assembly of SNSs is successful with a series of poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) block copolymers, and the size of NPVs can be tuned by changing their molecular weight. The polymer is easily extracted from the NPVs with their colloidal dispersibility and structural integrity intact. The polymer-free silica NPVs further serve as a reaction vessel and host for functional materials such as tin oxide nanoparticles.

Core–shell polymer–silica hybrid nanoparticles smaller than 50 nm in diameter were formed in the presence of micelles of poly­(2-aminoethyl vinyl ether-block-isobutyl vinyl ether) (poly­(AEVE m -b-IBVE n )) through the hydrolysis and polycondensation of alkoxysilane in aqueous solution at a mild pH and temperature. The size of the nanoparticles as well as the number and size of the core parts were effectively controlled by varying the molecular weight of the copolymers. The polymers could be removed by calcination to give hollow silica nanoparticles with Brunauer–Emmett–Teller surface areas of more than 500 m2 g–1. Among these, silica nanoparticles formed with poly­(AEVE115-b-IBVE40) displayed an anisotropy of single openings in the shell. The use of an alternative copolymer, poly­(AEVE-b-2-naphthoxyethyl vinyl ether) (poly­(AEVE113-b-βNpOVE40)), yielded core–shell nanoparticles with less pronounced anisotropy. These results showed that the degree of anisotropy could be controlled by the rigidity of micelles; the micelle of poly­(AEVE115-b-IBVE40) was more deformable during silica deposition than that of poly­(AEVE113-b-βNpOVE40) in which aromatic interactions were possible. This bioinspired, environmentally friendly approach will enable large-scale production of anisotropic silica nanomaterials, opening up applications in the field of nanomedicine, optical materials, and self-assembly.