Zr 1− x Ln x W 2 O 8− x /2 solid solutions (Ln=Eu, Er, Yb) of different substitution fractions x have been synthesized. Their X-ray diffraction (XRD) patterns have been indexed and lattice parameters calculated based on the α-ZrW 2 O 8 structure. The coefficients of thermal expansion (CTEs) of these solid solutions were estimated to be −10.3×10 −6 K −1 in temperature range of 30–100°C. The solubility of lanthanide ions in these solid solutions decreases linearly with the increase in the radius of substituted lanthanide ions. Based on the concentration dependence of phase transition temperatures, a novel method for determination of solubility of the lanthanide ions in Zr 1− x Ln x W 2 O 8− x /2 solid solutions has been developed. This method seems to be more sensitive as compared with that based on XRD technique.