We have performed first-principles calculations of the atomic and electronic structures and stability of three (α, β and γ) layered V2O5 phases and their free layers within the same computational approach. In computations, we have used a hybrid exchange–correlation functional within the density functional theory and a basis set of localized atomic orbitals. All the lattice parameters and the atomic positions have been totally optimized and the phonon frequencies at the Γ-point of the Brillouin zone have been obtained. The calculated relative stability of considered bulk phases decreases as α > γ > β. The calculated relative stability of layers differs from that of bulk phases and decreases as β > α ⩾ γ. The possibility of the folding of V2O5 layers into nanotubes is discussed.