An ideal signature material and method, which can be used to prove the authenticity of a physical item and against forgery, should be immune to the fast developments in digital and engineering technologies. Herein, the design of signature material combining cryptographic hash function and DNA steganography is proposed. The encrypting materials are used to construct a series of time-stamped records (blockchain) associated with published hash values, while each DNA-encrypted block is associated with a set of DNA keys. The decrypted DNA information, as digital keys, can be validated through a hash function to compare with the published hash values. The blocks can also be cross-referenced among different related signatures. While both digital cryptography and DNA steganography can have large key size, automated brutal force search is far more labor intensive and expensive for DNA steganography with wet lab experiments, as compared to its digital counterpart. Moreover, the time-stamped blockchain structure permits the incorporation of new cryptographic functions and DNA steganographies over time, thus can evolve over time without losing the continuous history line.