DNA is one of the most plentiful and naturally occurring helical polymers on earth. Recently, this ubiquitous helical polymer has gathered attention as a chiral source for asymmetric synthesis. In 2005 Feringa and Roelfes introduced the concept of DNA-based hybrid catalysts based on supramolecular assembly by using a copper complex of a nonchiral ligand that can bind to DNA. Since then, DNA-based hybrid catalysts have been applied to various key asymmetric carbon–carbon or carbon–heteroatom bond-forming reactions. Our group is exploring the potential of DNA for asymmetric synthesis. We have developed asymmetric intramolecular Friedel–Crafts alkylations using a supramolecular-assembled DNA hybrid catalyst. To understand the structural and mechanistic features of DNA-based asymmetric catalysis, we have established a systematic and modular strategy for the development of DNA hybrid catalyst based on the direct incorporation of an intrastrand bipyridine ligand into the DNA strand and demonstrated its application to the asymmetric reactions such as intramolecular Friedel–Crafts alkylations and enantioselective hydrations. In this talk, I will discuss our recent progress in the development and application of DNA-based hybrid catalyst for the asymmetric catalysis.