The chemistry of the on-water surface, characterized by enhanced reactivity, distinct selectivity, and confined reaction geometry, offers significant potential for chemical and materials syntheses. However, the utilization of on-water surface synthesis is currently limited by the requirement for a stable air-water interface, which restricts its broader synthetic applications. In this work, we present a approach that mimics on-water surface chemistry using micelles. This method involves the self-assembly of charged surfactant molecules beyond their critical micelle concentration (CMC), forming micellar structures that simulate the air-water interface. This creates an environment conducive to chemical reactions, featuring a hydrophobic core and surrounding water layer. Utilizing such mimicking on-water surface with the assembly of porphyrin-based monomers featuring distinct confined geometry and preferential orientations, we achieve reactivity and selectivity (≥99%) in fourteen different reversible and irreversible chemical reactions. Extending the versatility of this approach, we further demonstrate its applicability to two-dimensional (2D) polymerization on micellar interfaces, successfully achieving the aqueous synthesis of crystalline 2D polymer thin layers. This strategy significantly broadens the accessibility of on-water surface chemistry for a wide range of chemical syntheses.