Solid solutions of Zr(Mo,W)2O7(OH,Cl)2·2H2O with a preset ratio of components were prepared by a hydrothermal method. The chemical composition of the solutions was determined by energy dispersive X-ray spectroscopy (EDX). For all the samples of ZrMoxW2-xO7(OH,Cl)2·2H2O (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, and 2.0), TGA and in situ powder X-ray diffraction (PXRD) studies (300-1100 K) were conducted. For each case, the boundaries of the transformations were determined: Zr(Mo,W)2O7(OH,Cl)2·2H2O → orthorhombic-ZrMoxW2-xO8 (425-525 K), orthorhombic-ZrMoxW2-xO8 → cubic-ZrMoxW2-xO8 (700-850 K), cubic-ZrMoxW2-xO8 → trigonal-ZrMoxW2-xO8 (800-1050 K for x > 1) and cubic-ZrMoxW2-xO8 → oxides (1000-1075 K for x ≤ 1). The cell parameters of the disordered cubic-ZrMoxW2-xO8 (space group Pa-3) were measured within 300-900 K, and the thermal expansion coefficients were calculated: -3.5·10-6 - -4.5·10-6 K-1. For the ordered ZrMo1.8W0.2O8 (space group P213), a negative thermal expansion (NTE) coefficient -9.6·10-6 K-1 (300-400 K) was calculated. Orthorhombic-ZrW2O8 is formed upon the decomposition of ZrW2O7(OH,Cl)2·2H2O within 500-800 K.