Molecular recognition and drug delivery are crucial for diseases’ early diagnosis and targeted therapy. DNA, a natural nanoparticle, has good biocompatibility, molecular recognition characteristic, and sequence programmability, it has been widely concerned in biomedical researches. However, DNA nanomaterials depend on the photoresponsive systems and hard to penetrate the cytomembrane, these series of troubles make them difficult to meet the needs of complex experiments. Since DNA was identified to an excellent nanostructured building block, more and more new material systems assembled with DNA, a large number of DNA-metal nanomaterials have emerged especially, which endowed with photochemical property, tissue penetration ability and drug loading ability, overcoming the defects of a single material and showing great potential in biosensing, bioimaging and targeted drug delivery fields. Here, DNA-copper nanomaterials, DNA-upconversion nanomaterials and DNA-metal-organic framework nanomaterials are reviewed, because of unique photostability or high pore volumes of these 3 kinds of representative metal nanomaterials in the nanotechnology field. What’s more, they are low-cost and easily available. According to the combination ways of DNA and metal nanomaterials, these 3 DNA-metal nanomaterials are classified reasonably, and their the latest applications in biomedical field are introduced, in order to provide therapeutic ideas for the clinical prevention and treatment of cancer. Finally, the opportunities and challenges for DNA-metal nanomaterials are overviewed and discussed.