For exploring the multifold helical fabrication of polyoxometalate (POM)-based hybrid compounds, four POM-based crystalline compounds with different meso-helices, H-3[Ag-27(trz)(16)(H2O)(6)][SiW12O40](2)center dot 5H(2)O (1), H[Ag-27(trz)(16)(H2O)(4)][PW12O40](2)center dot 2H(2)O (2), [Ag-23(trz)(14)(H2O)(2)][HSiW12O40] (3), and [Ag-23(trz)(14)(H2O)(2)][PW12O40] (4), were successfully isolated by using the delicate 1,2,3-triazole ligand and silver ions in this work. Crystal analysis reveals that compounds 1 and 2 and compounds 3 and 4 are isomorphous and display 2-/4-fold mixed meso-helices and simple 2-fold meso-helices, respectively. In addition, due to the reversible multielectron redox behavior and electron storage functions of POMs, compounds 1 and 3 were studied as anode materials in lithium-ion batteries (LIBs). Compounds 1 and 3 show very high lithiation capacities (1356 and 1140 mAh g(-1), respectively) in the initial cycle, which are much higher than those of (NBu4)(4)[SiW12O40] and commercial graphite at the current density of 100 mA g(-1). More importantly, both compounds also show good stable performance after 100 cycles.