Four new phenylphosphonato SnR (R=Ph, Me) derivatives have been synthesized and characterized by infrared and Mössbauer spectroscopy. The structure of catena-poly[PhPOHSnMe] has been determined by single-crystal X-ray diffraction analysis. The Sn atoms are five-coordinated in all compounds, with the SnCO framework in a trans trigonal bipyramidal arrangement and the PhPOH anions being in axial positions. The molecular structure of [PhPOHSnMe] is arranged as a one-dimensional coordination polymer in which planar SnMe groups are axially bridged by -O-P-O- linkages of the PhPOH ligand. Neighboring chains are linked via O-H⋯O hydrogen bond interactions, generating a layered structure. In the RNH (PhPOH)SnR′ (R=Cy, Bu; R′=Ph, Me), the SnPh or SnMe residue is axially coordinated by two monodentate PhPOH. The role of the dialkylammonium cation, RNH, is crucial in the lattice building via a hydrogen bond network. These hydrogen bonds contribute to the crystal stability and compactness and result in a three-dimensional arrangement. The aqua complex PhPO(SnPh )·2HO has a discrete structure and the anion PhPO behaves as a bidentate ligand.