The tungsten substitution for molybdenum in cesium dimolybdate Cs2Mo2O7 with the formation of an α-Cs2Mo2−xWxO7 solid solution is studied, and its homogeneity region at 540 °C is found to reach 0 ≤ x ≤ 0.6. It is established that the volume of the monoclinic (pseudo-orthorhombic) unit cell and the solid solution melting point monotonically increase with increasing tungsten content, whereas the phase transition temperature to the orthorhombic phase remains practically constant and is ∼390 °C. The crystals of solid solutions with several compositions are obtained, their structure is determined, and the tungsten atoms are found to be mainly located in octahedral positions of the α-Cs2Mo2O7 structure. As a result of the phase transition at 390 °C the electrical conductivity of Cs2Mo2O7 increases approximately by two orders of magnitude reaching 1.2·10−4S/cm at 460 °C. Due to a large size of Cs+ ions and a high charge of molybdenum cations it is supposed that the charge carriers are oxygen anions. The calculation of bond valence sum (BVS) maps for possible positions of oxygen atoms in the α-Cs2Mo2O7 cell shows the formation of a 3D system of oxygen conductivity channels at boundary BVS isosurface values ≥ 2.13.