Due to the hierarchical structures, all-polymer hollow multishelled sphere (p-HoMS) possesses great potentials for diverse applications. To preserve self-supportive morphology, the multi-shells have to grow into thick ones for sufficient structural strength. And it is challenging to construct p-HoMS with nano-thin shells, facing difficulties in both spherical formation and shell separation. Herein, we propose a new synthetic mechanism, namely integrating strong rigidity with reaction-shrinkage of composite membranes. Rigid network is the backbone for spherical formation, while reaction-shrinkage fast separates shells. The obtained p-HoMS is tunable in shell number up to 70 shells with nanoscale thickness (60–140 nm). This work can provide a novel insight for the easy fabrication of hierarchical p-HoMS and guide the rational structure design towards diverse demands.

由于分层结构，全聚合物空心多壳球体（p- HoMS）在各种应用中具有巨大的潜力。为了保持自支撑形态，多壳必须长成厚壳以获得足够的结构强度。构建具有纳米薄壳的p -HoMS具有挑战性，在球形形成和壳分离方面都面临困难。在此，我们提出了一种新的合成机制，即将强刚性与复合膜的反应收缩相结合。刚性网络是球形形成的支柱，而反应收缩快速分离壳。得到的p-HoMS 的壳数可调，可达 70 个具有纳米级厚度（60-140 nm）的壳。这项工作可以为分层p- HoMS的轻松制造提供新的见解，并指导合理的结构设计满足不同的需求。