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PROBLEM TO BE SOLVED : To provide a method for easily producing a bulky clathrate compound in a high yield. SOLUTION : A compound of a group IVB element of the periodic table containing one or more elements selected from among alkali metal, alkaline earth metal, rare earth element and transition metal is melted or finely crushed in an inert atmosphere, maintained at a temp. of >=500 deg.C for >=10 hr, cooled, washed top remove excess alkali metal, alkaline earth metal, rare earth element or transition metal and formed by hot-pressing. An intercalant graphite interlayer compound may be used as the compound of a group IVB element of the periodic table containing one or more elements selected from among alkali metal, alkaline earth metal, rare earth element and transition metal.