Preface of the special issue of the Journal of Physical Chemistry in conjunction with the international workshop "Aqueous Solutions and their Interfaces". The topics include the structure of liquid water, the analysis of X-ray and neutron scattering experimental data, the vibrational spectroscopy of liquid water, the structure and spectroscopy of aqueous interfaces and the development of theoretical approaches to model the structure and spectra of liquid water and interfaces. This work was supported by the US Department of Energy's Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.