The synthesis of a novel first stage GIC containing simultaneously lithium, potassium and barium through a solid–liquid reaction by molten salts method is described. Such a route has been largely developed in our laboratory for intercalation of metals into graphite. The interplanar distance of this quaternary compound reaches 950 pm and exhibits poly-layered intercalated sheets defined by X-ray measurements. The Li0.2K0.75Ba0.6C6 chemical formula of the compound is determined by ion beam analysis and this GIC is remarkably homogeneous. This GIC is the first poly-layered one containing barium.