A novel Zr1-xFexV2-xMoxO7 (0 <= x <= 0.9) material is developed and the effect substitutions of Fe3+/Mo6+ for Zr4+/V5+ in ZrV2O7 on the thermal expansion property are investigated. For the smaller x value (x <= 0.5), their crystal structures remain cubic. The one of x = 0.5 is much higher than recent reports about uni-substitution of P5+ for V5+ and dual-substitution of Cu2+/P5+ for Zr4+/V5+. For a substitution more than 0.5, crystal lattice appears distorted and 3 x 3 x 3 superstructure disappears gradually. For the substitution of x = 0.9, low thermal expansion is obtained from 140 to 700 K, which holds great potential applications in low temperature field. The mechanism of low thermal expansion of Zr1-xFexV2-xMoxO7 (0 <= x <= 0.9) is discussed around the distortion of crystal structure due to the substitutions of Fe3+/Mo6+ for Zr4+/V5+ in ZrV2O7. Crown Copyright (C) 2015 Published by Elsevier B.V. All rights reserved.