(ZrCa)xY2-2xW3O12(x =0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0) are developed with a simple solid state method, and characterized for crystal structure, hygroscopicity and thermal expansion by X-ray diffraction, Raman spectroscopy, thermal analysis and dilatometer. The results show that the hygrosopicity of solid solution decreases obviously, and the coefficient of thermal expansion (CTE) changes regularly after complete release of the crystal water with the increase of (ZrCa)6+ content. A near-zero thermal expansion (ZTE) is realized for (ZrCa)0.6Y0.8W3O12 as x=0.6, and the linear CTE (al) is measured to be 2.79×10-7 K-1(453~1 000 K).