Fluoride (F-)-substituted B-type carbonate hydroxyapatite (CHAP) powders were prepared for application as bone substitute materials having the ability to enhance bone formation and to suppress bone resorption due to the therapeutic effect of F-. F- was adsorbed on CHAP in a sodium fluoride solution followed by heating at 700 degrees C in carbon dioxide flow to substitute F- for the hydroxyl ion in the CHAP structure. The F- contents in the F-substituted CHAP powders were 16-22 times greater than that in normal adult human bones. The carbonate ion contents in the F-substituted CHAP powders corresponded to or were higher than that in normal adult human bones. F-substituted CHAP powder with CO3(2-) and F- contents of 11.03 and 0.66 wt%, respectively, slowly released F- in a physiological salt solution to a sufficiently high F- level. The F- concentration slowly increased and reached 67.20 +/- 4.81 microg l(-1), which was 1.5-9.3 times higher than that in the body fluid of normal adult humans, near the therapeutic window of F-, and far lower than the estimated toxic level. Therefore, the F-substituted CHAP can promote bone formation. The present F-substituted CHAP has the advantage of slow F- release over sodium fluoride and sodium monofluorophosphate which are highly soluble salts and cannot be sintered into a ceramic body.