ZnO/vermiculite as the novel photocatalysts were prepared by two approachs: one is mixtures of ZnO and different acid treated vermiculite, and another is sol-gel method. The acid activated vermiculite as a new promising catalyst support and adsorbent has a large capacity of absorption, high surface area and thermal stability. The activity of catalyst has been interrelated to support and ZnO. Based on the important effect of support on ZnO/vermiculite photocatalysts, treatment of vermiculite by nitric acid of different concentration was studied by evaluated in the photocatalytic decomposition of MB with resulting photocatalysts. BET surface area measurement and X-ray diffraction (XRD) analysis were used to characteristic of ZnO particle in acid treated vermiculite structure and the phase structure and crystallization index of ZnO in the modified vermiculite mineral. Results showed the ZnO-vermiculite combination possessing higher photocatalytic activity due to the synergistic effect when compared to the commercial ZnO.