There is a definite overlap between the concepts of molten salts and ionic liquids; however, the present tendency is to use “molten salts” to characterize melts of purely inorganic compounds. If theoretical modeling of ionic crystals is relatively easy to achieve from X-ray diffraction data in view of the periodic arrangements of ions in the structure, it becomes a much more involved process when molten salts are considered because of interparticle interactions due to collisions. A single experimental technique usually gives a partial picture of the situation only so that a multiple-technique approach has to be used combining for instance X-ray diffraction, vibrational spectroscopy, density measurements, molecular dynamics, and Monte Carlo calculations. The review first focuses on the definition of the radial distribution function and on the ways to estimate coordination numbers in the first and second shell from this function. It then describes the present knowledge for melts of rare-earth and alkali halides and further on concentrates on salts with polyatomic anions. The penetration of ions from the second into the first coordination sphere is discussed as well as the formation of polymeric ions and their clustering. Kinetic aspects are also given attention.