This study evaluated the effect of sodium trimetaphosphate (TMP) associated or not with fluoride (F) on the structure and dissolution of carbonated hydroxyapatite (CHA). Synthetic CHA powder (1.0 g) was suspended in solutions containing TMP at 0-10%, associated with 0, 1100, 4500, or 9000 ppm F, and the precipitates were submitted to a pH cycle (n = 6/group). Samples were analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. F, calcium (Ca) and phosphorous (P) concentrations were determined in CHA, while P and F were analyzed in the supernatants. Data were submitted to analysis of variance, Student-Newman-Keuls' test and Pearson's correlation coefficient (α = 0.05). Solutions containing 1100 ppm F with TMP between 2-4% and 4500 and 9000 ppm F with TMP between 4 and 8% led to higher Ca/P ratio (p < 0.05) in CHA. Alkali-soluble F deposition was directly related to TMP concentrations whereas an inverse pattern was observed for acid-soluble F incorporation (p < 0.05). Greater P adsorption in the CHA structure was observed with increasing concentrations of TMP for the 0 and 1100 ppm F solutions (p < 0.05). All diffractograms and FTIR spectra showed a similar pattern to that for pure hydroxyapatite. Thus, when TMP and F are coadministered, TMP interferes with F deposition on CHA, and an ideal TMP:F ratio can enhance the precipitation of CHA with lower solubility. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 2553-2564, 2018.