Two novel compounds, namely, [(H(2)toym)(4)(Mo8O26)(2)]center dot 15H(2)O (1) and [(H(2)toym)(2)(SiW12O40)]center dot 6H(2)O (2) (toym = 2,4,6-tris[1-(4-oxidroxypyridinium)-ylmethyl]-mesitylene), have been hydrothermally synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses, and UV-Vis absorption spectra. Compounds 1 and 2 exhibit new supramolecular networks templated by polyoxometalates (POMs). The "host'' supramolecular networks with large pores are composed of the partly protonated toym ligands for 1 and 2. The "guest'' POMs are located in the pores and dispersed between two organic layers in the complexes. The luminescent properties for 1 and 2 have been studied. In addition, compounds 1 and 2 exhibit photocatalytic activities for methylene blue (MB) degradation under UV. (C) 2013 Elsevier B.V. All rights reserved.