A novel hybrid layered material-Schiff Base-Zinc Complexes intercalated ZnCr-LDHs-supported ZnO-was synthesized by one-step coprecipitadon method and characterized by XRD, UV-vis DRS, SEM, TEM, BET, ICP-AES and XPS analysis. The influences of the three Zn components (intercalated between the layers, supported on the surface, distributed in the host layers of the layered material) on the crystallinity and the photocatalytic activity of ZnO/ZnCr-SalenZn-LDHs for Rhodamine B (RhB) degradation were studied in detail by orthogonal design. The results showed that the percentage of the three components has a great effect on the structure and photocatalytic performance of ZnO/ZnCr-SalenZn-LDHs. The SalenZn intercalated between the layers and the Zn distributed in the layers of the layered material were the main influencing factors, and the ZnO supported on the surface of the layered material was the secondary influencing factor. The optimum initial molar ratios were SalenZn:Cr = 0.5, Zn:Cr = 3, and ZnO:Cr = 0.75, respectively, and the photocatalytic degradation efficiency of RhB reached 96.9%. In addition, a possible mechanism of photocatalysis was discussed from the perspectives of photogenerated reactive species and photoinduced carries transfer. While, the regeneration of the best photo catalytic material was also investigated in detail.