Synthesis and characterization of negative thermal expansion HfW2−xVxO8−x/2 solid solutions

► Novel cubic HfW2−xVxO8−x/2 solid solutions and their precursors were synthesized. ► Cubic HfW2−xVxO8−x/2 solid solutions show excellent negative thermal expansion. ► The relationship between the properties of the samples and the V content is revealed. ► x up to 0.34, a rare large solid solubility in aliovalent substitution.