The action of MCl2-AlCl3molten salt systems (M˭Cu, Cd, Pd, Co) does not permit the intercalation into graphite the heteromolecules MAl2Cl8which exist in the liquid. All these molten chloroaluminate reagents give intercalated species which correspond to an AlCl3layer with low divalent ionic content the basal plane structure of which appears to be dependent on the divalent metal. In the case of copper, palladium and cobalt, this 2D order corresponds to a hexagonal cell (a=600pm) whose study based on the experimental and calculated (hko) intensities suggests a substitutional process between the Al3+and M2+ions in the intercalated layers.