The soft interfacial template-assisted confined self-assembly of block copolymers (BCPs) guiding colloidal aggregates has been extensively investigated by interfacial instability. Whether the macromolecular polymer architectonics possessed stimulus-responsive self-regulated structural controllability more readily implement the morphological diversity of colloidal aggregates. Herein, we in-situ constructed the alginate-modified β-cyclodextrin/azobenzene-functionalized alkyl chains (Alg-β-CD/AzoC12) system by supramolecular host–guest interfacial recognition-engineered strategy, in which possessed photo-stimulated responsive structural reconfigurability by modulating assembly/disassembly behaviors between CD and Azo at oil/water interface. The host–guest droplet interfaces acted as soft templates managing interfacial instability by synergistically integrating supra-amphiphilic host–guest polymers with cosurfactants, further constructing various soft supracolloidal aggregates, including soft nanoaggregates, microspheres with tunable degrees of surface roughness. Additionally, the stimuli-altering structural reconfigurability of supramolecular host–guest polymers was regulated by ultraviolet/visible irradiation, endowing soft aggregates with structural diversity. It’s highly anticipated that the supramolecular host–guest interfacial recognition self-assembly establishes great bridge between supramolecular host–guest chemistry and colloid interface science.