Three new complex fluorides of trivalent titanium have been isolated from the products of electrolysis, under an inert atmosphere, of molten baths of KC1, NaCl, or mixtures of KCl and NaCl, containing either K2TiF6 or Na2TiF6. Electrolytic baths containing a mixture of KCl and NaCl with either K2TiF6 or Na2TiF6 yielded a violet-colored, face-centered cubic compound identified as K2NaTiF6, which was virtually insoluble in water and amenable to electrostatic separation from the metallic titanium also produced in the electrolysis. Baths containing molten mixtures of K2TiF6 and KCl gave a pale violet compound K3TiF6, which was slightly soluble in water. Baths containing Na2TiF6 and NaCl gave a deep violet-colored compound Na3TiF6 which was almost insoluble in water. The compounds K3TiF6 and Na3TiF6 have structures which approximate to cubic. The compounds K2NaTiF6 and Na3TiF6 are more stable to atmospheric oxidation than is K3TiF6. X-Ray diffraction patterns have been recorded for these compounds and some of their physical and chemical properties determined.