Abstract: Metal phosphonates nanosheets and nanorods were prepared from the reaction of three metal precursors, including aluminium hydroxide, ferric hydroxide and zinc acetate, with phenyl or diphenyl phosphonates without the assistance of templates. Structures of materials were characterized by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis (TGA), scanning electron microscopy(SEM), powder X-ray diffraction (XRD), demonstrated a structure of Me—O—P(Me=Al, Fe, Zn) main chains and the existence of π−π stacking, which enabled the assembly into nanorod and nanosheets. The results show that the dimension of nanostructure is largely determined by phosphonate precursors rather than metal centers. Two-hydroxyl functionality tends to generate a layered nanostructure, while one-hydroxyl functionality results in nanorod structure. TGA spectra show that when organophosphonic ligands are incorporated into the hybridized materials, their thermal stability is significantly improved.