Compartmentalized
micelles (CMs) are promising tailor-made soft
matters that mimic natural designed structures and functions. Despite
the structure of complex CMs, manipulating CM structures accessibly
and reversibly remains elusive. Here, we report the fabrication of
CMs via a generally valid noncovalent postmodification process. Starting
from precursor micelles (PMs) based on one diblock copolymer, aromatic
modification leads to the compartmentalization of PMs into well-defined
spherical CMs. Control over compartment number, size and distribution
in CMs, and segment distribution in their linear hierarchical assemblies
is attained by simply tuning the postmodification degree and solvent
composition. We also demonstrate the reversible transformation between
PM and CMs during several heating–cooling cycles, which endows
the micelles with potential in reversible functional transitions in situ close to nature’s capability. Moreover, both
hierarchically assembled or ill-structured micelles can rearrange
into homogeneous CMs after one heating–cooling cycle, featuring
the postmodification guided compartmentalization strategy with unprecedented
micelle reproducibility.