Bismuth molybdenum hydrous oxide was prepared by water-thermally direct precipitation in relatively concentrated solutions. The composition of the resulting product was Bi2Mo3O12·3.86H2O determined by thermal analysis and ICP. The X-ray powder diffraction pattems of the crystal synthesized was identical with that of Bi2Mo3O12·4.75H2O. Pyridine, 2,5-dimethylpyridine and 4-benzylpiridine were intercalated into inorganic crystal, significantly expanding interlayer distance alongb axis in the monoclinic cell unit of bismuth molybdenum hydrous oxide. The organic molecules were intercalated by solvent exchange mechanism which mainly devoted to the expansion of interlayer spacing.