Nanoporous phospho-tungstate organic–inorganic hybrid materials have been synthesized from sodium tungstate and mono-n-dodecyl phosphate (MDP), which was used as both surfactant and phosphorus precursor. These hybrid materials were thoroughly characterized by N₂ adsorption, elemental analysis, powder XRD, FTIR, Raman, TG, TEM and XPS and possess lamellar structures with interlayer spacings of 3.2 nm. A plausible method for formation of hybrid materials comprised of lacunary Keggin anions and micelles of surfactants is proposed.