Low thermal expansion materials are mostly ceramics with low conductive property, which limits their applications in electronic devices. The poor conductive property of ceramic ZrV2O7 could be improved by bi-substitution of Fe and Mo for Zr and V, accompanied with low thermal expansion. Zr0.1Fe0.9V1.1Mo0.9O7 has electrical conductivity of 8.2× 10?5 S/cm and 9.41× 10?4 S/cm at 291 K and 623 K, respectively. From 291 K to 413 K, thermal excitation leads to the increase of carrier concentration, which causes the rapid decrease of resistance. At 413–533 K, the conductivity is unchanged due to high scattering probability and a slowing increase of carrier concentration. The conductivity rapidly increases again from 533 K to 623 K due to the intrinsic thermal excitation. The thermal expansion coefficient of Zr0.1Fe0.9V1.1Mo0.9O7 is as low as 0.72× 10?6 K?1 at 140–700 K from the dilatometer measurement. These properties suggest that Zr0.1Fe0.9V1.1Mo0.9O7 has attractive application in electronic components.