Two novel POM-based inorganic organic hybrids, [Cul(6)(II)(2,2'-bipy)(6) (Mo6O22) (SiW12O40)](n) (1), and {[Cu-6(II)(ppz)(6)(H2O)(5) (MoO4) (SiW12O40)]center dot 4H(2)O}(n) (2) (2,2'-bipy = 2,2'-bipyridine, Hppz = 3-(pyrid-2-yl)pyrazole), have been constructed from heteropolytungstates and molybdates. Two compounds have been identified by single crystal X-ray diffraction, elemental analysis, and FT-IR. Compound 1 shows a 1D (one-dimensional) chain structure constructed from classical Keggin heteropolytungstate [SiW12O40](4-) clusters and [Cu-6(2,2'-bipy)(6)] modified isopolymolybdates [Mo6O22](8-). Compound 2 also represents a ID chain-like motif built from classical Keggin heteropolytungstate [SiW12O40](4-) clusters and [Cu-8(ppz)(6)(H2O)(5)] modified molybdates MoO42-. Compound 1 represents the first example of POM-based inorganic-organic hybrid with mixed heteropolytungstates and isopolymolybdates. ESI-MS (electrospray ionization mass spectrometry) technique was employed to reveal the species and their evolutions in the hydrothermal reaction, whereby trivacant [SiW9] building block gradually transforms to classical Keggin [SiW12] during assembly process. Furthermore, the electrocatalytic and magnetic properties were discussed in details.