By using the in situ generated octamolybdate as an inorganic building block and tuning the spacer length of the flexible bis(triazole) ligands, three coordination polymers with different architectures, [Cu-II(btp)(2)(H2O)(beta-Mo8O26)(0.5)]center dot H2O (1) (btp 1,3-bis(1,2,4-triazol-1-yl) propane), [Cu-2(II)(btb)(3)(H2O)(2)(z-Mo8O26)]center dot 3H(2)O (2) (btb 1,4-bis(1,2,4-triazol-1-yl) butane), and [Cu-II(bth)(2)(theta-Mo8O26)(0.5)]center dot H2O (3) (bth 1,6-bis(1,2,4-triazol-1-yl) hexane) were synthesized and structurally characterized. Compound 1 displays 2-fold interpenetration architecture, in which the [beta-Mo8O26](4-) polyanions act as pillars between the stagger-packed [Cu(btp)(2)](2+) sheets. Compound 2 exhibits parallel-packed 2D layers with the [zeta-Mo8O26](4-) polyanions encircled by chair-type [Cu(btb)(2)](2+) rings. For compound 3, there exist quadrangular channels in the 3D network constructed from the [Cu(bth)(2)](2+) cations. The [theta-Mo8O26](4-) polyanions are incorporated into the channels, resulting in a novel interpenetrated 3D architecture with (4(2)center dot 6(11 center dot)8(2))(4(2)center dot 6(4))(4(4)center dot 6(10)center dot 8) topology. Thermogravimetric analyses and electrochemical measurements for all the compounds were also performed.