Negative thermal expansion (NTE) material ZrWMoO8 was prepared by hydrothermal method. The phase structure and morphology of the obtained precursor and final product were examined by XRD and SEM, respectively. To study its negative thermal expansion property, two methods were utilized. One is based on the in-situ XRD results and the thermal expansion coefficient (CTE) was calculated by the cell parameters obtained at different temperatures. Another is based on the thermo-mechanical analysis (TMA) and the CTE was calculated by the length of ZrWMoO8 bar at different temperatures. The differences between these two methods were also discussed.