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Three rare-earth-containing heteropolyoxometalates with different sizes, Na9[Eu(W5 O18)2], K13[Eu(SiW11O39)2], and K17[Eu(P2W17O61)2], have been incorporated by self-assembly into the interlayer of synthetic multibilayer films of dimethyldioctadecylammonium chloride and exhibited different orientations.