A Raman study of ferric chloride hexadydrate (FCHH) in 11.5M HCl solutions has shown the presence of tetrahedral FeCl4− ion as the most prominent species. An appreciable concentration of a polymeric species, which is composed of higher chloroferrate groups of the type FeCl5 · H2O, and a small concentration of lower chloro-aquoferrate complex ion of the type Fe(H2O)4Cl2+ are also present in the solutions. The saturation of FCHH-11.5M HCl solution with dry HCl is observed to convert both the polymeric species and the lower chloro-aquoferrate ions into FeCl4− ions. In hydrated ferric chloride melts the most prominent species exists in the form of tetrahedral FeCl4− ion along with an appreciable concentration of Fe(H2O)4Cl2+ ion. Hydrated ferric chloride melts saturated with LiCl or dry HCl gas, contains only FeCl4− ions. In the case of moderately acidic (≤ 6M HCl) ferric chloride solutions Raman evidence has revealed the presence of a polymeric species along with significant concentrations of lower chloro-aquoferrate complexes. For neutral ferric chloride solutions evidence indicates that the most prominent species exists in the form of a polymeric species with structural characteristics similar to those observed in moderately acidic solutions. It has been proposed that these polymeric species are composed of randomly oriented higher chloroferrate groups of the type FeCl5 · H2O and FeCl6. Higher stability of the polymeric species in the neutral solutions has been attributed to the presence of a strong hydration layer around the polymeric species.