An improved synthesis using microwave heating affords (C6H4PO(OCH3)2)2 in excellent isolated yield (95 %). The ligand properties of this bisphosphonateester were explored towards hard metal centers M2+ (M = Ca, UO2) and M3+ (M = La, Ce, Sm, Eu) resulting in coordination polymers, for which the reduction of ionic size of the central metal atom resulted in lower-dimensional structural motifs as opposed to higher dimensional networks obtained for the larger ions. All coordination polymers were characterized by single-crystal X-ray diffraction, IR spectroscopy, and combustion analysis. The ligand was furthermore characterized with multinuclear NMR spectroscopy.