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Cubic ZrMo 2-x V x O 8-x/2 (0 B x B 0.5) compounds, with well-defined nanorods morphology, were synthesized by a facile sol-gel process without using any surfactant or template. The resulting products were characterized by the X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermal mechanical analyzer and UV-vis diffuse reflectance spectra (UV-vis DRS). The results indicated that V-doping did not influence the crystal structure and negative thermal expansion (NTE) property, but made rods size increase. Narrowed band gap was observed in V-doped ZrMo 2 O 8 . The resultant V-doped ZrMo 2 O 8 samples, as compared with pure ZrMo 2 O 8 , exhibited improved UV-light photocatalytic activity, during the photocatalytic degradation of rhodamine B. The mechanism was supposed that the V-doping gave rise to the formation of oxygen vacancies which could enhance photocatalytic performance by reducing the recombination of electrons and holes. In addition, cubic ZrMo 2-x V x O 8-x/2 also displayed reliable recycling photocatalytic performance and satisfying UVlight catalytic activity for the organic pollutant. Furthermore, all of the resulting cubic ZrMo 2-x V x O 8-x/2 showed excellent NTE property from 25 to 450°C. Graphical Abstract TEM images of (a) pure ZrMo 2 O 8 and (b) ZrMo 1.7 V 0.3 O 7.85 ; (c) RhB degradation under UVlight illumination for 180 min in the presence of cubic ZrMo 2-x V x O 8-x/2 (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5) photocatalysts.