A wide range of polyvanadates can be synthesized from aqueous solutions. Vanadium oxide gels V2O5nH2O are formed around the point of zero charge (pH≈2). They exhibit a ribbon-like structure. Weak interactions between these ribbons lead to the formation of mesophases in which vanadium oxide gels or sols behave as nematic liquid crystals. Organic species can be easily intercalated between these oxide ribbons leading to the formation of hybrid nanocomposites made of alternative layers of organic and inorganic components. Hybrid nanophases can also be formed above the point of zero charge, in the presence of large organic ions such as [N(CH3)4]+. They often exhibit layered structures in which organic cations lie between the polyvanadate planes. Cluster shell polyvanadates have been obtained in the presence of anions such as Cl− or I−. They are made of negatively charged polyvanadate hollow spheres in which the anion is encapsulated. Organic cations then behave as counter ions for the formation of the crystal network.