Aqueous solutions of sodium tribromoacetate (NaCBr 3CO 2) and its corresponding acid (CBr 3COOH) have been studied using Raman and infrared spectroscopy. The spectra of the species in solution were assigned according to symmetry C s. Characteristic bands of CBr 3CO 2 −(aq) and the tribromoacetic acid, CBr 3COOH(aq), are discussed. For the hydrated anion, the CO 2 group, the symmetric CO 2 stretching mode at 1332 cm −1 and the asymmetric stretching mode at 1651 cm −1 are characteristic while the C O mode at 1730 cm −1 is characteristic for the spectra of the acid. The stretching mode, νC–C at 912 cm −1 for CBr 3CO 2 −(aq) is 10 cm −1 lower in the anion compared with that of the acid. These characteristic modes are compared to those in acetate, CH 3CO 2 −(aq). Coupling of the modes are fairly extensive and therefore DFT calculations have been carried out in order to compare the measured spectra with the calculated ones. The geometrical parameters such as bond length and bond angles of the tribromoacetate, and tribromoacetic acid have been obtained and may be compared with the ones published for other acetates and their conjugated acids. CBr 3COOH(aq) is a moderately strong acid and the p K a value derived from quantitative Raman measurements is equal to −0.23 at 23 °C. The deuterated acid CBr 3COOD in heavy water has been measured as well and the assignments were given.