A novel cubic ZrW2-xVxO8-x/2 solid solution series was found to possess similar negative thermal expansion property like the extensively studied ZrW2O8. A tetragonal hydrate ZrW2-xVxO7-x/2 (OH)(2)(H2O)(2) up to x = 0.30 was first prepared through acidic steam hydrothermal synthesis, this precursor dehydrates at moderate temperature and converts to an intermediate orthorhombic phase then transforms to corresponding solid solutions at higher temperature. At room temperature cubic ZrW2-xVxO8-x/2 (x = 0-0.24) has alpha-ZrW2O8 type and ZrW1.70V0.30O7.85 has beta-ZrW2O8 type disordering. X-ray diffraction, neutron diffraction and Raman spectroscopy studies support an average crystal structure model of ZrW2-xVxO8-x/2 as a superposition of respective cubic ZrW2O8 and ZrV2O7 structures. The lattice parameters of cubic ZrW2-xVxO8-x/2 solid solutions, the value of orientation order parameter omega and order-disorder phase transition temperature of the solid solutions all decrease with increasing substitution content x. The maximum solid solubility of cubic ZrW2-xVxO8-x/2 solid solution reaches 16% according to the Vegard's law. (C) 2012 Elsevier B.V. All rights reserved.