Hydrated molybdenum bronzes have been prepared by reduction reaction of MoO3 with NaBH4 in ethanol and DMSO. The reduction reactions in both solvents occur smoothly; thus, the layered structure of MoO3 is maintained in the product. Divalent cation Ca2+ has been intercalated between the MoO3 layers, which leads to highly reduced molybdenum bronze (Mo5.26+). Solvated molybdenum bronze catalyzes the reduction reaction of DMSO by NaBH4, producing CH3SCH3. The structure model of hydrated sodium molybdenum bronze has also been reinvestigated by using the Rietveld analysis. The hydrated molybdenum bronze crystallizes in an orthorhombic structure, in which the structure of Mo octahedron layers is closely related to that in MoO3. However, the structure refinement reveals that the Mo octahedron in the MoO3 layers is axially distorted, which is different from that in MoO3 but similar to an isoelectron compound H0.33MoO3.