New Scheelite-related solid solutions of the compositions Nax/2Bi1-x/2MoxV1-xO4 (0 less than or equal to x less than or equal to 1) and Bi1-x/3 MoxV1-xO4(0 less than or equal to x less than or equal to 0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO, type ferroelastic BiVO4. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Nax/2Bi1-x/2MoxV1-xO4, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi1-x/3 MoxV1-xO4 where 0 less than or equal to x less than or equal to 0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.