Intercalation compounds NbOXO4· 2CnH2n+1OH (X=P, As; andn=2–18) and NbOXO4· CnH2n(OH)2(n=2–10) have been prepared. The molecules of alcohols are placed between the host layers in a bimolecular way, being anchored to them by donor–acceptor bonds between the oxygen atom of an OH group and a niobium atom as well as by hydrogen bonds. The molecules of diols are arranged in a monomolecular way and form bridges linking the adjacent layers of the host. The aliphatic chains of the guest molecules possess theall-transconfiguration and are inclined with respect to the host layers. The stability of the intercalates of NbOPO4with 1-tetradecanol and 1,10-decanediol has been studied by XRD as a function of temperature and by thermogravimetry.