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, [CuII(btp)2(H2O)(β-Mo8O26)0.5]·H2O (1) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane), [CuII2(btb)3(H2O)2(ζ-Mo8O26)]·3H2O (2) (btb = 1,4-bis(1,2,4-triazol-1-yl)butane), and [CuII(bth)2(θ-Mo8O26)0.5]·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 [β-Mo8O26]4−polyanions act as pillars between the stagger-packed [Cu(btp)2]2+ sheets. Compound 2 exhibits parallel-packed 2D layers with the [ζ-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 [θ-Mo8O26]4−polyanions are incorporated into the channels, resulting in a novel interpenetrated 3D architecture with (42·611·82)(42·64)(44·610·8) topology. Thermogravimetric analyses and electrochemical measurements for all the compounds were also performed.