Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy‐polyethyleneglycol‐monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid‐state MAS NMR techniques. The organic components of the phosphates have been characterized by the 13C{1H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates. The MAS NMR experiments including kinetics of proton‐phosphorus cross polarization have resulted in an unusual structure of zirconium phosphate 6 combining decoration of the phosphate surface by polymer units and their partial intercalation into the interlayer space. Copyright © 2016 John Wiley & Sons, Ltd.