Three novel carboxyarylphosphonate polymers {[Zn 2 (PCP)(H 2 PCP)(phen) 2 ]·H 2 O} n (1), [Zn(HPCP)(4,4Ј-bipy)] n (2), and [Zn 33and phen = phenanthroline] were synthesized and characterized by single-crystal X-ray diffraction. Compound 1 features a butterfly-shaped dimer consisting of [Zn 4 P 4 O 10 ] 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