A novel photocatalytic ZrWMoO8/Ag composite with core-shell structure was prepared. The composites were composed of ZrWMoO8 rods with negative thermal expansion (NTE) property as cores and Ag nanoparticles as shell. The resulting products were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV-visible spectrophotometer (UV-vis DRS). The results showed that ZrWMoO8 rods displayed not only negative thermal expansion but also photocatalytic efficiency toward Rhodamine B (RB) degradation under UV-irradiation. The as-prepared ZrWMoO8/Ag composites exhibited a higher photocatalytic activity than that of pure ZrWMoO8, thereby implying that the ZrWMoO8/Ag interfaces promote the separation of photogenerated electron-hole pairs and enhance the photocatalytic activity. (C) 2012 Elsevier B. V. All rights reserved.