UiO-66(Ce) was prepared from cerium metal, which could trigger Fenton-like reactions. A system DOX@UiO-66(Ce)@TA-Fe was constructed by coating a metal polyphenol layer (TA-Fe) on the surface of DOX@UiO-66(Ce), which was loaded with the anticancer drug doxorubicin hydrochloride (DOX). It could produce reactive oxygen species to realize chemodynamic therapy and show stimuli-responsive drug release behaviors to realize chemotherapy. In addition, the system displayed biocompatibility to normal cells (L929 cells) and toxicity to cancer cells (MCF-7 cells), implying an ideal effect for multimodal cancer therapy.