Compounds Yb2Mo3O12 and Lu2Mo3O12 were prepared by conventional solid-state reaction. Their crystal structures and thermal expansion properties were investigated. It was found that Yb2Mo3O12 and Lu2Mo3O12 adopt orthorhombic structure and show negative thermal expansion (NTE) in the temperature range of 200-800 °C. Their a-axis and c-axis exhibit stronger contraction in the temperature range of 200-800 °C, while b-axis slightly expands in the temperature range of 200-300 °C and then contracts in the temperature range of 300-800 °C. The linear thermal expansion coefficients al of Yb2Mo3O12 and Lu2Mo3O12 are −5.17 × 10−6 °C−1 and −5.67 × 10−6 °C−1, respectively.