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High-purity ZrWMoO8 powder was prepared by a precursor decomposition method. To prepare ZrWMoO8/Cu composite, the blended powder of Cu and ZrWMoO8 as well as the copper-coated ZrWMoO8 powder with m(ZrWMoO8):m(Cu)=1:1 were obtained by ball-milling and chemical plating method, respectively. And then the two sorts of the powders were pressed into green specimens which were sintered in argon atmosphere at 500 °C for 3 h to get ZrWMoO8/Cu composites. The thermal expansion properties of the composites were studied, and it is found that the coated-powder is much more suitable for the preparation of ZrWMoO8/Cu material. Results show that after sintering, a part of the ZrWMoO8 is decomposed and reacted with copper in the composite obtained by the blended-powder. While the decomposition of ZrWMoO8 is not detected in the composite obtained with copper-coated ZrWMoO8 powder as raw materials and the composite displays an average thermal expansion coefficient of 3.3774×10-6 °C-1 between 25~250 °C and the relative density is as high as 90.6%.