Four Preyssler P5W30 based inorganic organic hybrids, formulated as {[Cu-12(pbtz)(2)(Hpbtz)(2)(OH)(4)(H2O)(16)] [Na(H2O)P5W30O110]}center dot 16H(2)O (1; H(2)pbtz = 5'-(pyridin-2-yl)-1H,2'H-3,3'-bi(1,2,4-triazole)), {[Cu-10(ttbz)(2)(Httbz)(4)(OH)(6)(H2O)(8)][K(H2O)H2P5W30O110]}center dot 30H(2)O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni-6(bpz)(6)(H2O)(16)][Na(H2O)-H2P5W30O110]}center dot 36H(2)O (3; bpz = 3,3',5,5'-tetramethyl-4,4-bipyrazole), {[Co-4(bpz)(6)(H2O)(9)][K(H2O)H(6)P(5)W(30)O(11)0]}center dot 46H(2)O (4), have been isolated and structurally identified via microanalysis, thermogravimetry (TG), infrared (IR) spectroscopy, and X-ray single-crystal diffraction. Compound 1 exhibits a 3D binodal (3,6)-connected ant framework composed of dodeca-supported P5W30 polyoxometalate (POM) clusters and discrete [Cu-6(pbtz)(Hpbtz)(OH)(2)(H2O)(8)] subunits. Compound 2 is a pillared-layer 3D network constructed from [Cu-5(ttbz)(Httbz)(2)(OH)(3)(H2O)(4)] sheets pillared by individual P5W30 clusters. Compound 3 contains octa-supporting P5W30 POM clusters and novel [Ni-6(bpz)(6)] crown-like metallamacrocycles, which construct a (4,4)-connected pts network. Compound 4 displays a complicated 3D (5,5)-connected {4(5).6(4).8}{4(5).6(5)} network built by pentasupporting P5W30 POM clusters and discrete [Co-4(bpz)(6)(H2O)(9)] subunits. In 1-4, the unified features are the Preyssler-type [P5W30O110] POM as the fundamental building block, which supports the transition-metal compounds with different modes to give the resultant diverse networks. The magnetism studies indicated antiferromagnetically coupled systems for the hexa- and pentanuclear Cu(II) units in 1 and 2, respectively. The electrochemical properties demonstrate that all compounds have electrocatalytic abilities toward the reduction of hydrogen peroxide. Furthermore, the catalytic activities of 1 in the cyanosilylation of aldehydes reaction have been investigated.