A monomeric tellurotungstate(iv)-supported rhenium carbonyl derivative: Na2H2[(CH3)4N]6[Te2W20O70{Re(CO)3}2]·20H2O (1) has been successfully isolated and structurally characterized by single crystal X-ray diffraction crystallography, IR and UV-Vis spectroscopy, thermogravimetric analysis, etc. In particular, complex 1 could act as a efficient and reusable heterogeneous catalyst for selective epoxidation of various alkenes including different cycloalkenes, styrene derivatives, internal and long-chain alkenes. For example, cis-cyclooctene undergoes up to 98.2% conversion and >99% selectivity at 75 °C in acetonitrile with 30% H2O2 as an oxidant. Additionally, the electrocatalytic property of 1 for NO2- reduction was also investigated.