Rapid and selective removal of micropollutants from water is the global issue for reuse of water resources. Despite hollow frameworks with specific functionalized porous walls have been used for the selective adsorption based on a series of interactions, tailoring a stable shape of nano- and micrometer-sized architectures for the removal of specific pollutants remains a challenge. Here, exactly controlled sheets, tubes, and spherical frameworks were presented from the crosslinking of supramolecular colloids in polar solvent. The frameworks strongly depended on the architectures of original supramolecular colloids. As the entropy of colloids increased, the initial

laminar framework rolled up into hollow tubules, and then further curled into ultima hollow spheres. These shape-persistent frameworks showed unprecedented selectivity as well as specific recognition for the shape of pollutants, which contributed to efficient pollutant separation.