Cubic ZrW 2− x Mo x O 8 (c-ZrW 2− x Mo x O 8 ) (x=0–1.3) solid solutions were prepared by a novel polymorphous precursor transition route. X-ray diffraction (XRD) analysis reveals that the solid solutions are single phase with α- and β-ZrW 2 O 8 structure for 0⩽x⩽0.8 and 0.9⩽x⩽1.3, respectively. The optimum synthesis conditions of ZrWMoO 8 are obtained from differential scanning calorimetry–thermal gravimetric analysis (DSC–TGA), XRD and mass loss-temperature/time curves. Following the above experience, the stoichiometric solid solutions of c-ZrW 2− x Mo x O 8 (x=0–1) are obtained within 1wt% of mass loss. The relationships of lattice parameters (a), phase transition temperatures (T c ) and instantaneous coefficients of thermal expansion (α i ) against the content x of Mo are discussed based on the variation of order degree parameters of ZrW 2− x Mo x O 8 .