A hybrid inorganic-organic assembly, NaH3(C6H5NO2)4[GeW12O40] · 7H2O (1), has been synthesized and characterized by IR, UV, 1H NMR and single crystal X-ray diffraction. Crystal data: orthorhombic, P212121, a = 12.819(2) Å, b = 19.326(3) Å, c = 24.164(4) Å, V = 5986.4(18) Å3, Z = 4, R1 = 0.0541 (I > 2σ). The structure of 1 is based on a 1D zigzag infinite chain assembled by alternating [GeW12O40]4- and sodium-pyridine-2-carboxylic complex [Na(C6H5NO2)3(H2O)2]+ via W-Od-Na-Od-W.