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In this paper, CdS QDs@ZrO 2 –TiO 2 hollow spherical composites with double Z-scheme heterostructure modified by CdS QDs were prepared by the sol–gel method and vacuum impregnation method using polystyrene (PS) microspheres synthesized by the self-assembly technique as templates. A series of characterization results show that CdS QDs@ZrO 2 –TiO 2 composites treated by PS microspheres have the structure of hollow spheres with uniform size and orderly arrangement. Moreover, the double Z-scheme heterojunction formed between CdS QDs, ZrO 2 , and TiO 2 in the composite can optimize the charge transfer path and improve the charge separation efficiency. Results of the photodegradation and the photo-splitting water of CdS QDs@ZrO 2 –TiO 2 composites show that, compared with other systems, CdS QDs@ZrO 2 –TiO 2 composites have the highest photocatalytic degradation rate of crystal violet, and meanwhile, the photocatalytic hydrogen production rate of the composite under simulated sunlight is more than 100 times that of TiO 2. The good absorption of visible light, the successful construction of double Z-scheme heterojunction, and the unique hollow sphere structure of CdS QDs@ZrO 2 –TiO 2 composites are the key factors for enhanced photocatalytic performance. The preparation of CdS QDs@ZrO 2 –TiO 2 hollow spherical composite material with PS microspheres as templates not only expands its photoresponse range, but also optimizes the charge transfer path and improves the separation efficiency of electron–hole pairs by the construction of double Z-scheme heterojunction. [Display omitted] • CdS QDs@ZrO 2 –TiO 2 hollow spherical composite was prepared using PS microspheres as templates. • Hollow spherical CdS QDs@ZrO 2 –TiO 2 is not only uniform in spherical size, but also in neat and orderly arrangement. • Successful construction of double Z-scheme heterojunction improves charge separation efficiency. • The addition of CdS QDs expands the visible light response range. • CdS QDs@ZrO 2 –TiO 2 exhibits the highest photocatalytic activity compared with TiO 2 , @TiO 2 , and @ZrO 2 –TiO 2. [ABSTRACT FROM AUTHOR]