Abstract: The development of high-performance memristors meets the needs of the era of big data. In particular, memristors that use organic/polymer materials with flexibly adjustable structures as the active layer are becoming increasingly popular in the field of photoelectric sensing and artificial intelligence. Inspired by mussel-inspired chemistry, a polydopamine (PDA) film was self-assembled on indium tin oxide(ITO)-coated glass substrate to form an active layer, and then grafted azobenzene (Azo) with photoisomerization properties through click chemistry to prepare the memristive device with the structure of Al/PDA-Azo/ITO, and its photoelectric performance has been studied. As a result, Azo molecules are covalently grafted on the surface of polydopamine. The as-prepared device exhibits stable nonvolatile rewritable memory characteristics under applied voltage scanning. The conductivity of the device increases by 30 times after UV light irradiation, and it can be recovered after visible light irradiation, indicating that the fabricated memoristor achieves photoelectric dual response.