Two novel hydrated inorganic-organic hybrids, namely [L-C2H5NO2-H](3)[H2BW12O40]center dot 5H(2)O (1) and [CH4N2O-H](2)[H3BW12O40]center dot 5H(2)O (2), where C2H5NO2 and CH4N2O are glycine and urea, respectively, have been synthesized and characterized by CHN microanalysis, IR, UV, and H-1 NMR spectroscopies. According to the obtained results, molecular structure of 1 consists of tungstoborate anions linked to glycinium cations via van der Waals interactions and hydrogen bonding. Three [L-C2H5NO2-H](+) moieties encompass each [H2BW12O40](3-) and, almost certainly, the same is true for 2. The O atoms of polyoxometalates and water, as well as the N atoms of L-glycine and urea are involved in hydrogen bonding. Characteristic UV bands of the Keggin anion, alpha-H-5[BW12O40]center dot 19H(2)O, are observed at 257 mn, as would be expected.