Mechanisms for carrier generation in zinc antimonate (ZnSb2O6) with a wide band gap were examined in relation to its crystallinity. ZnSb2O6 prepared by the reaction of Sb2O5 sol and 3ZnCO(3)center dot 4Zn( \OH)(2) was sintered at 893, 1173, and 1393 K, and characterized by X-ray diffraction (XRD), electrical conductivity and diffuse reflectance measurements. A higher conductivity was found for ZnSb2O6 sintered at lower temperatures. Rietveld analysis of XRD patterns showed that the cations in conductive ZnSb2O6 occupied irregular sites, similar to the random rutile structure. Electron carriers were also considered to be generated by oxygen vacancies in ZnSb2O6 samples which have a structure similar to the random rutile structure.