Super-reduction of polyoxometalates (POMs) in solution is of fundamental interest for designing innovative energy storage systems. In this article, we show that the “Dawson-like” POM can undergo a disproportionation process during its massive electron uptake, leading to species containing three metal-metal bonds as evidenced by X-ray diffraction, multi-nuclear magnetic resonance spectroscopy (1H and 183W NMR), extended X-ray absorption fine structure (EXAFS), UV/Vis, and voltammetry techniques. This result indicates that electron storing within metal-metal bonds is not a unique property of Keggin-type POM as postulated since the 70s. Besides, we demonstrate that the presence of an electron-rich triad in the “Dawson-like” POM allows its post-functionalization with additional tungstate ions, generating a chiral molecule that is also the largest WIV-containing POMs known to date.