Two novel supramolecular complexes [Na(B30C10)][Mo₆O₁₉] (1) and [NaL(CH₃CN)][NaL][α-PMo₁₂O₄₀][NaL₂] (L＝B15C5) (2) were synthesized based on B15C5 and polymolybdates by hydrothermal techniques and characterized by X-ray diffraction analysis. Single crystal X-ray diffraction indicates that complex 1 belongs to monoclinic, C2/m, and consists of three basic units: Na^＋, B15C5 and Mo₆O . The crown ethers coordinate with Na^＋, and connected with polyoxometalate by static force. Complex 2 crystallizes in the triclinic space group P-1 and contains an [α-PMo₁₂O₄₀]^3－ anion and three sodium complexes, [Na(B15C5)]^＋ connected through Mo—O—Na—O bond.

Key words: B15C5, polymolybdates, hydrothermal, crystal structure, assembly