The homogeneous and seed-assisted precipitation of dicalcium phosphate dihydrate (DCPD or brushite) and hydroxyapatite (HAP) under controlled supersaturation regimes in chloride media at room temperature (22 degrees C) is investigated. Prior to their reactive crystallization the metastable zones of precipitation for the two calcium orthophosphates were determined. The effects of supersaturation, reaction time, and seeding on the stoichiometry and crystallinity of these compounds were studied. Acidified solutions (pH approximate to 2.0) of NaH2PO4 (2-90 mmol/L) and CaCl2 (2-150 mmol/L) were mixed in order to get Ca to P molar ratios in initial solution of 1.0 or 1.67 (the stoichiometric ratios for dicalcium phosphate dihydrate and hydroxyapatite).The supersaturation in solution was built up by the slow addition of 100 mmol/L NaOH solution. In seed-assisted precipitation tests (Ca/P = 1) the metastable calcium phosphate solution (37.5 mmol/L) was neutralized until the precipitation pH of 5 was reached and 10 g/L of seed was added. The homogeneous precipitation of DCPD at pH 5.4 was fast and equilibrium was reached in 30 min. In the presence of seed, the precipitation rate was slower due to reduced supersaturation. Even so, in both cases well crystalline plate-like crystals matching the stoichiometry of brushite were produced. Calcium-deficient hydroxyapatite with nanocrystalline structure (nanocrystallite size similar to 20 nm) was produced at pH 7.6 under controlled supersaturation. The homogeneously produced material consisted of irregularly shaped agglomerates of the order of 5-15 mu m while the product obtained by seed-assisted precipitation was in the form of rather coarse (ca. 20-30 mu m) and dense spheroids. The highest Ca:P ratio material (Ca:P = 1.58) was obtained with seed-assisted precipitation at a slow addition rate.