Alternately amidated poly(1-carboxylate-3-N-alkylamidotetramethylene)s (alkyl = t-Bu, n-Bu) were synthesized from poly(acrylic anhydride) and alkylamines as ligands for Ca(II) complexes. The anion form of the alternately amidated polycarboxylates possesses an NH C) hydrogen bond between the carboxylate oxygen and the adjacent amide NH. The reinforcement of Ca-O bond strength by the NH . . .O hydrogen bond, upon the mineralization of calcium carbonate, is maintained at the interface between crystalline CaCO3 and the polymer ligands because it prevents the removal of the alternately amidated poly(1-carboxylate-3-N-alkylamidotetramethylene) ligand from the crystalline CaCO3 under neutral conditions. Under the same conditions, a commercial poly(acrylate) ligand readily releases Ca(II) ion to separate from the surface of the crystal by hydrolysis with water. The binding carboxylate ligand C-13 on calcium carbonate is detectable using solid-state C-13 CP/MAS spectroscopy.