In this study, bismuth sulfide (Bi2S3)‐doped cerium oxide (CeO2) was prepared via hydrothermal method, and by depositing ethyl 3,4‐dihydroxybenzoate (EDHB) on the surface of Bi2S3/CeO2 (Bi2S3/CeO2/EDHB and BCE). The samples were characterized by FTIR, XRD, TEM, and UV–vis absorption spectrum means. According to the characterizations, Bi2S3 was successfully incorporated into the CeO2 structure (Bi2S3/CeO2), and the prepared BCE/PVC composite films display excellent UV‐shielding property. Moreover, the result of thermogravimetric analysis (TGA) tests indicated that BCE also was barely catalytic thermal decomposition of PVC matrix. This work not only paves an attractive way for the design of the CeO2‐based UV‐shielding agent, but also provides valuable insights into the inspiration to construct high‐performance UV‐shielding composites.