We first prepared tetragonal Zr(W1-yMoy)(2-x)VxO7-x/2(OH)(2)center dot 2H(2)O (y = 0.10, 0.20, 0.30, 0.40; 0 <= x <= 0.40) hydrate precursors through acidic steam hydrothermal (ASH) treatment. Dehydration of these precursors produces the corresponding low temperature orthorhombic polymorph Zr(W1-yMoy)(2-x)VxO8-x/2. Upon annealing at 813-873 K for 2 h this intermediate further transforms to the end product of kinetically favored cubic Zr(W1-yMoy)(2-x)VxO8-x/2 solid solutions. The dehydration and orthorhombic to cubic phase transition temperatures decrease linearly with increasing Mo and constant V content; the orthorhombic to cubic phase transition temperature also decreases linearly with increasing V content at constant W/Mo ratio. Measurements of thermal stability and expansion indicate that cubic Zr(W1-yMoy)(2-x)VxO8-x/2 solid solutions have strong negative thermal expansion property. We characterized the average structure of c-Zr(W0.90Mo0.10)(1.76)V0.24O7.88 using Rietveld refinement method, calculated lattice parameters of solid solutions and solid solubility at different y value, and discuss structural factors that affect cell parameter values. (C) 2014 Elsevier B.V. All rights reserved.