A three-dimensional polymolybdate-based metal-organic framework (POMOF) consisting of Zn-epsilon-Keggin unit and organic linker, {[(PMo8Mo4O37)-Mo-V-O-VI (OH)(3)Zn-4][BPE](2)}center dot[BPE] (1), was successfully obtained by the hydrothermal method. Compound 1 is composed of Zn-epsilon-Keggin units and BPE ligands, featuring a fascinating 5-fold interpenetrating framework with dia topology. The catalytic performance of compound 1 was investigated, and experiments showed that 1 could effectively facilitate the cycloaddition reaction of CO2 with epoxides as Lewis acid heterogeneous catalyst. Moreover, compound 1 also was studied as LIBs anode material, and it showed reversible capacity of 546 mA h g(-1) at 100th cycle.