One pot reactions of phenylphosphonic acid or phenylarsonic acid with cyclohexylamine led to two new organic-inorganic hybrid salts [C6H14N][C6H5PO3H.C6H5PO3H2.H2O] (1) and [(C6H14N)(C6H5AsO3H)] (2) which were investigated by single-crystal X-ray diffraction analysis. Salt 1 crystallizes in the monoclinic system, space group P21/nwith a = 12.3963 (4), b = 6.1123 (2), c = 28.2081 (8) Å, β = 90.426 (1)°, V = 2137.27 (12)Å3 and Z = 4. Salt 2 crystallizes in the monoclinic system, space group P21/c with a = 12.3991 (5), b = 6.5048 (2), c = 18.5466 (7) Å, β = 105.824 (2)°, V = 1439.16 (9) Å3 and Z = 4. In the co-crystal 1, the hydrogen phenylphosphonate anions are organized into dimers via O–H···O H-bonds, whereas the phenylphosphonic acid and the water molecules are connected, through Owater–H···O and O–H···O hydrogen bonding interactions, to form dimers. Inter-species O–H···O hydrogen bonds connect the alternating dimers into anionic infinite chains. The 1D infinite ribbons are linked into an anionic 2D layer-like structure, by means of water molecules through Owater–H···O and O–H···Owater. The cyclohexylammonium interacts via N–H···O hydrogen bonds, to consolidate the compactness of the 2D layer-like structure. In the crystal of salt 2, the hydrogen phenylarsonate anions are organized into dimers through O–H···O H-bonds. Hydrogen bonded dimers are connected by the cyclohexylammoniumcations, through N–H···O hydrogen bonds, leading to the formation of an infinite ribbon. The 1D hydrogen bonded ribbons are interlinked through N–H···O hydrogen bonding interactions giving rise to a 2D layer-like structure.