Thermally and hydrolytically unstable di-tert-butyl phosphate (dtbp-H) has been used as synthon to prepare discrete and polymeric calcium phosphates that are convenient single-source precursors for a range of calcium phosphate ceramic biomaterials. The reactivity of dtbp-H toward two different calcium sources has been found to vary significantly, e.g., the reaction of Ca(OMe)(2) with dtbp-H in a 1:6 molar ratio in petroleum ether forms a mononuclear calcium hexa-phosphate complex [Ca(dtbp)(2)(dtbp-H)(4)] (1), whereas the change of calcium source to CaH2, in a 1:2 molar ratio under otherwise similar reaction conditions, yields the calcium phosphate polymer, [Ca(mu-dtbp)(2)(H2O)(2)center dot H2O](n) (2). Compounds 1 and 2 have been extensively characterized by various spectroscopic and analytical techniques. The solid-state structures of both 1 and 2 have been determined by single-crystal X-ray diffraction studies. In discrete molecule 1, the central calcium ion is surrounded by two anionic dtbp and four neutral dtbp-H ligands in an octahedral coordination environment. Compound 2 is a one-dimensional polymer in which adjacent calcium ions are connected through double dtbp bridges. Solid-state thermolysis of bulk 1 in air leads to the exclusive formation of calcium metaphosphate beta-Ca(PO3)(2) in the entire temperature range of 400-800 degrees C. Thermal decomposition of polymer 2, however, can be fine-tuned to produce either alpha-Ca(PO3)(2) or beta-Ca(PO3)(2) depending on the thermolysis conditions employed. Although the sample sintered at 600 degrees C produces exclusively alpha-form of Ca(PO3)(2), the sample annealed at 800 degrees C or above produces beta-form. Both alpha- and beta-forms can also be successively formed one after other by a slow heating of a freshly prepared 2 on the powder diffractometer sample holder. Additional forms of ceramic phosphates have been prepared by solvothermal conditions because of the highly labile nature of the tert-butoxy groups of dtbp in 1 and 2. Solution decomposition of either 1 or 2 in boiling toluene at 140 degrees C in a sealed tube produces calcium dihydrogen phosphate [Ca(H2PO4)(2)center dot H2O] as the only product in the form of single crystals. Solution thermolysis of 2 in protic solvents such as water and methanol can be biased to produce other calcium phosphate biomaterials such as hydroxyapatite [Ca-10(PO4)(6)(OH)(2)]and calcium monohydrogen phosphate [Ca(HPO4)] in the presence of additional calcium precursors such as CaO and Ca(OMe)(2), respectively.