The reaction of picolinic acid (Hpic) and (n-Bu4N)4[MosO26] in the presence of CH3CN gave a supramolecular compound (n-Bu4N)2[Mo2O6(pic)2] (1), and its structure was characterized by elemental analysis, IR spectra and single crystal Xray diffraction analysis. The single crystal X-ray diffraction study shows that the crystal is in monocnnic crystal system, P21/c space group with cell parameters a=0.9941 (2), b=1.3719(2), c=1.8824(2)nm, β=100.840(10)°, Mr=508.50, V=2.5214(9)nm3, F(000)=1072. Compound 1 is a dimer through two μ2-O bridging to two MoO3 (pic)-unit, then connected one-dlmensional anion-chain by undassical hy-drogen bonding, and the anion-chain across the channels formed via (n-Bu4N)+ cations. By means of undassical hydrogen bonding, the anion-chain and cationchannels assemble into three-dimensional supramolecular networks.