A new inorganic-organic hybrid material based on polyoxometallate, [L-C2H6NO2](3)[(PO4)Mo12O36]center dot 5H(2)O has been successfully synthesized and characterized by single-crystal X-ray analysis, elemental analysis, infrared and ultraviolet spectroscopy, proton nuclear magnetic resonance and differential thermal analysis techniques. The title compound crystallizes in the monoclinic space group, P2(1)/c, with a = 12.4938 (8) angstrom, b = 19.9326 (12) angstrom, c = 17.9270 (11) angstrom, beta = 102.129 (1)degrees, V= 4364.8 (5) angstrom(3), Z = 4 and R-1 (wR(2)) = 0.0513, 0.0877. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/infinity [PO4)Mo12O36](3-)) which forming via weak Van der Waals interactions along the z axis. The characteristic band of the Keggin anion [(PO4)Mo12O36](3-) appears at 210 nm in the UV spectrum. Thermal analysis indicates that the Keggin anion skeleton begins to decompose at 520 degrees C. (C) 2007 Elsevier Ltd. All rights reserved.