Due to the increasing energy density demands of battery technology, it is vital to develop electrolytes with high electron storage capacity. Polyoxometalate (POM) clusters can act as electron sponges, storing and releasing multiple electrons and have potential as electron storage electrolytes for flow batteries. Despite this rational design of clusters for high storage ability can not yet be achieved as little is known about the features influencing storage ability. Here we report that the large POM clusters, {P5W30} and {P8W48}, can store up to 23 e−and 28 e−per cluster in acidic aqueous solution, respectively. Our investigations reveal key structural and speciation factors influencing the improved behaviour of these POMs over those previously reported (P2W18). We show, using NMR and MS, that for these polyoxotungstates hydrolysis equilibria for the different tungstate salts is key to explaining unexpected storage trends while the performance limit for {P5W30} and {P8W48}, can be attributed to unavoidable hydrogen generation, evidenced by GC. NMR spectroscopy, in combination with the MS analysis, provided experimental evidence for a cation/proton exchange process during the reduction/reoxidation process of {P5W30} which likely occurs due to this hydrogen generation. Our study offers a deeper understanding of the factors affecting the electron storage ability of POMs and provides insights allowing for further development of these materials for energy storage.