The application of DNA-based hybrid catalysts for enantioselective synthesis has recently emerged. These catalysts, self-assembled from DNA and a metal complex with a specific ligand through supramolecular or covalent anchoring strategies, have demonstrated high enantioselectivity in a variety of carbon-carbon or carbon-heteroatom bond-forming reactions and have expanded their role in asymmetric catalysis. In this review, we summarize the advent and significant progress of DNA-based asymmetric catalysis and discuss remaining challenges in using DNA as a chiral scaffold. We hope that this review will inspire many of today’s active scientists in asymmetric catalysis.