The novel supramolecular networks based on Keggin-type polyoxoanion, formulated (Hpy)3[PMo12O40]·2(py) has been synthesized hydrothermally and determined by X-ray diffraction. The compound crystallize in Monoclinic, system with space groups and cell parameters, P2 1 /n, a = 10.9370(2) A, b = 19.586(3) A, c = 12.5500(2) A, β = 98.618(2)°, V = 2657.8(6) A3. Organic fragments and Keggin anions are connected via N–H···N, N–H···O contacts to form interesting 1D zigzag chain. The molecule is stabilized in solid state by electrostatic forces and intermolecular hydrogen-bonding interactions to give the confirmation of guest [PMo12O40]3− inserting in organic host. The novel supramolecular networks based on Keggin-type polyoxoanion, formulated (Hpy)3[PMo12O40]·2(py) has been synthesized hydrothermally and determined by X-ray crystal diffraction. 1D zigzag chain is formed by N–H···N, N–H···O interactions between organic fragments and Keggin anions. The molecule diverse assembling patterns as 3D supramolecular networks of guest [PMo12O40]3− inserting in organic host.