The oxidation power of permanganates (MnO4-) is known to be strongly dependent on pH values, land is greatly enhanced in acidic solutions, in which, for example, MnO4- can even oxidize Cl- ions to produce Cl-2 molecules. Although such dependence has been ascribed due to the different reduced states of Mn affordable in different pH media, a molecular level understanding and characterization of initial redox pair complexes available irt different pH. Solutions is very limited. Herein, we report a comparative study of [MnO4-] and [MnO4 center dot Sol](-) (Sol = H2O, KCl, and HCl) anion dusters by negative ion photoelectron Spectroscopy (NIPES) and theoretical computations to probe chemical bonding and electronic structures of [MnO4-center dot Sol](-) clusters, aimed to obtain a microstopie understanding of how MnO4- interacts with surrounding molecules. Our study shows that H2O behaves as a solvent molecule, KCl is a spectator bound by pure electrostatic interactions, both of which do not influence the MnO4- identity in their respective clusters. In contrast, in [MnO4 center dot HCl](-), the proton is found to interact with both MnO4- and Cl- with appreciable covalent characters, and the frontier MOs of the cluster are comprised of contributions from both MnO4- and Cl- moieties. Therefore, the proton serves as a, chemical bridge, bringing-two negatively charged redox species together to form an intimate redox pair. By adding more H+ to MnO4-, the Oxygen atom can be taken away in the form of a water molecule, leaving MnO4- as an electron deficient MnO3+ species, which can subsequently oxidize Cl- ions.