Developing a new field of molecular self-assembly in the sub-micrometer regime-with precision as high as that used to make discrete nano-sized molecular architectures through molecular design-is a major challenge for supramolecular chemistry. At present, however, there is no effective strategy for controlling the assembling molecules when their quantity is greater than one thousand. Herein, we propose a potential solution by exploiting a novel supramolecular system in conjunction with dynamically shrinking oil droplets, enabling more than a thousand component molecules to organize simultaneously into the form of sub-micrometer-scale ring structures. In our developed system, amphiphilic porphyrins, having potential two-dimensional assembling ability, were compartmentalized into droplets with narrow distributions and molecular numbers. These droplets were subsequently transformed into discrete ring-like structures during the process of solvent removal from the inner organic layer, i.e., shrinking the droplets. Unique self-assembled structures, which are not accessible through conventional supramolecular strategies, can be selectively created depending on the initial stage of the droplet.