We experimentally investigate effects of W6+ occupying the sites of Sc3+ in the unit cell of Sc2W3O12 (Sc8W12O48)on the structure,vibration and thermal expansion.The composition and structure of the doped sample (Sc6W2)W12O48±δ(with two W6+ occupying two sites of Sc3+ in the unit cell of Sc8W12O48) are analyzed and identified by combining the x-ray photoelectron spectroscopy and the synchronous x-ray diffraction with first-principles calculations based on density functional theory.Results show that the crystal with even W6+ occupying even Sc3+ in the unit cell is stable and maintains the orthorhombic structure at room temperature.The structure of the doped sample is similar to that of Sc2W3O12,and with even W occupying even positions of Sc in the unit cell and constituting the WO6 octahedra.Raman analyses show that the doped sample possesses stronger W-O bonds and wider Raman linewidths than those of Sc2W3O12.The sample doped with W also exhibits intrinsic negative thermal expansion in the measured range of 150 K-650 K.