The monoclinic (space group C2/m) superstructure of V14O6, which is formed in the atom–vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is studied by the methods of x-ray diffraction and symmetry analysis. It has been found that the channel of the order–disorder phase transition attributed to the formation of the monoclinic suboxide V14O6 includes six superstructure vectors belonging to three non-Lifshitz stars {k1−1}, {k1–2}, and {k1–3} of one type {k1}. The distribution function of the O atoms in the V14O6 monoclinic superstructure has been calculated. It has been shown that the displacements of V atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the fcc sublattice and the transition from the suboxide V14O6 to the cubic vanadium monoxide with the B1 structure.