The important concepts of supermolecular chemistry have been applied for the construction of the supermolecular catalysis systems. The development on supermolecular catalysts has great significance for not only the design of novel catalysis systems but also the understanding of catalysis mechanisms. In the beginning of the 20th century, enzymes were successfully isolated and used as biocatalysts outside living cells. Multifunctional enzyme means that the enzyme is functionalized in multiple ways to synthesize more than one kind of products. Enzyme engineering employs approaches of either rational design or directed evolution to modify enzyme properties, which is often a time-consuming process. Mainly mimic enzymes, the field of supermolecular catalysis has grown significantly, providing new tools for selective transformations. Various materials, including polymers, inorganic substances, and supramolecular assemblies, as well as a wide range of catalysts or enzymes, may be assembled in layer-by-layer structures.