A new 12-tungstovanadate-templated 3D nanocage framework, Ag-10(mu(4)-ttz)(4)(H2O)(4)(VW12O40) (VW12@MOCF), was designed based on a "molecular library", hydrothermally synthesized, structurally characterized, and explored as anode material for lithium-ion batteries (LIBs). Combination of the structural superiority of VW12@MOCF with the good electrical conductivity of the single-walled carbon nanotubes (SWNTs) renders the VW12@MOCF/SWNT-2 nanocomposite reasonable electrochemical performance and stability as anode materials of LIBs. The successful cooperative fabrication of nanocages and polyoxometalate (POMs) must initiate extensive research interests.