A new mixed valence phase Bi6V3O16 has been prepared and characterized. The structure has been determined by Rietveld method, from powder diffraction data using synchrotron radiation, in the orthorhombic space group Pnma (a = 5.4721(1)Å, b = 17.2542(3)Å, c = 14.9174(2)Å). The structure derives from the Aurivillius basic type, where (Bi2O2)2+ layers alternate with layers with composition (VO3.33)2− best described by (V3O10)6− ribbons running along the a axis. These ribbons contain units built up from an octahedron (VIV) and two tetrahedra (VV).