A series of remarkable crystalline compounds containing metallapillararene/metallacalixarene metal-organic frameworks (MOFs), [Ag-5(pyttz)(3)center dot Cl center dot(H2O)][H3SiMo12O40]center dot 3H(2)O (1), [Ag-5(trz)(6)][H5SiMo12O40] (2), [Ag-5(trz)(6)] [H5GeMo12O40] (3), and [Ag-5(trz)(6)] [H4PW12O40] (4) (pyttz = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, trz = 1,2,4-triazole), have been obtained by using a simple one-step hydrothermal reaction of silver nitrate, pyttz for 1 and trz for 2-4, and Keggin type polyoxometalates (POMs). Crystal analysis reveals that Keggin POMs have been successfully incorporated in the windows of the metallapillararene/metallacalixarene MOFs in compounds 1-4. In addition, the Keggin silicomolybdenate-based hybrid compounds 1 and 2 were used as anode materials in lithium ion batteries (LIBs), which exhibited promising electrochemical performance with the first discharge capacities of 1344 mAh g(-1) for 1 and 1452 mAh g(-1) for 2, and this stabilized at 520 mAh g(-1) for 1 and 570 mAh g(-1) for 2 after 100 cycles at a current density of 100 mA g(-1). The performances are better than that of (NBu4)(4)[SiMo12O40] matrix and commercial graphite anodes.