Density-functional tight-binding (DFTB) models are computationally efficient approximations to density-functional theory that have been shown to predict reliable structural and energetic properties for various systems. In this work, the reliability and accuracy of the self-consistent-charge DFTB model and its recent extension(s) in predicting the structures, binding energies, charge distributions, and vibrational frequencies of small water clusters containing polyatomic anions of the Hofmeister series (carbonate, sulfate, hydrogen phosphate, acetate, nitrate, perchlorate, and thiocyanate) have been carefully and systematically evaluated on the basis of high-level ab initio quantum-chemistry [MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVQZ] reference data. Comparison with available experimental data has also been made for further validation. The self-consistent-charge DFTB model, and even more so its recent extensions, are shown to properly account for the structural properties, energetics, intermolecular polarization, and spectral signature of hydrogen-bonding in anionic water clusters at a fraction of the computational cost of ab initio quantum-chemistry methods. This makes DFTB models candidates of choice for investigating much larger systems such as seeded water droplets, their structural properties, formation thermodynamics, and infrared spectra. © 2014 Wiley Periodicals, Inc.