To investigate the relationship between the structures of polyoxometalate host-guest materials and their energy-storage performance, three novel polyoxometalate-based metal-organic compounds, [Ag10(C2H2N3)8][HVW12O40], [Ag10(C2H2N3)6][SiW12O40], and [Ag(C2H2N3)][Ag12(C2H2N3)9][H2BW12O40] are synthesized by a one-step hydrothermal method and further confirmed by single-crystal X-ray diffraction analyses and other numerous characterization techniques. In compound [Ag10(C2H2N3)8][HVW12O40], the Keggin clusters are intersected into channels formed by a 3D open metal-organic framework. In contrast, in compounds [Ag10(C2H2N3)6][SiW12O40] and [Ag(C2H2N3)][Ag12(C2H2N3)9][H2BW12O40], the Keggin clusters are encapsulated into silver-triazole metal-organic nanocages to construct core-shell structures, which are further fused together by covalent bonds to form 3D polyoxometalate-based metal-organic frameworks. The electrochemical properties of three compound-based electrodes are estimated by cyclic voltammetry, galvanostatic charge-discharge, electrochemically active surface area, and electrochemical impedance spectroscopy. The results of the electrochemical performance tests indicate that these compounds possess high specific capacitance and cycling stability, especially [Ag10(C2H2N3)8][HVW12O40], showing a specific capacitance of 93.5 F g-1, which is higher than that of many other polyoxometalate-based electrode materials. A possible mechanism of the electrochemical performance is explored, which is mainly related to the redox capacity of polyoxometalate, the electrochemically active surface area, the electrochemical impedance spectroscopy, and the microstructures of polyoxometalate-based metal-organic frameworks.