The crystal structure, phase transition and thermal expansion behaviors of solid solutions Sc2-xCrxMo3O12 (0 <= x <= 2) were investigated using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). At room temperature, samples with x <= 0.7 and x >= 0.8 crystallize in orthorhombic and monoclinic structures, respectively. DSC result indicates that the phase transition of Sc0.5Cr1.5Mo3O12 from monoclinic to orthorhombic structure occurs at 203.66 degrees C. The linear thermal expansion coefficient of orthorhombic phases varies from -2.334 x 10(-6) degrees C-1 to 0.993 x 10(-6) degrees C-1 when x increases from 0.0 to 1.5. The near-zero linear thermal expansion coefficients of -0.512 x 10(-6) degrees C-1 and 0.466 x 10(-6) degrees C-1 are observed for compounds with x = 0.5 and 0.7, respectively. (c) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.