Three　novel　carboxyarylphosphonate　polymers　{[Zn2(PCP)(H2PCP)(phen)2]·H2O}n　(1),　[Zn(HPCP)(4,4′-bipy)]n　(2),　and　[Zn3(MCP)2(2,2′-bipy)]n　(3)　[PCP3–　=　p-O2C(C6H4)CH2PO33–,　MCP3–　=　m-O2C(C6H4)CH2PO33–　and　phen　=　phenanthroline]　were　synthesized　and　characterized　by　single-crystal　X-ray　diffraction.　Compound　1　features　a　butterfly-shaped　dimer　consisting　of　[Zn4P4O10]　tetranuclear　units,　which　are　further　linked　by　hydrogen　bonds　and　π–π　stacking　interactions　into　a　3D　supramolecular　framework.　In　2,　there　is　an　infinite　P–O–Zn　inorganic　2D　(4,4)　layer　with　the　phosphonate　moieties　of　HPCP2–　and　unidentate　4,4′-bipy　ligands　vertically　sticking　out.　As　for　3,　the　novel　[Zn6P4O12]　hexanuclear　units　with　＇chair＇　conformation　are　tetrahedrally　bridged　by　eight　MCP3–　to　generate　a　2D　double-layer,　in　which　the　windows　are　occupied　by　2,2′-bipy　molecules.　Additionally,　2D　correlation　analysis　of　FTIR　with　thermal　perturbation　of　3　were　discussed.　Compounds　1–3　exhibit　intense　solid　state　fluorescent　emissions.　Thermogravimetric　analyses　suggested　the　very　high　stability.　©　2019　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim