The oxidation power of permanganates (MnO4(-)) is known to be strongly dependent on pH values, and is greatly enhanced in acidic solutions, in which, for example, MnO4(-) can even oxidize Cl(-) ions to produce Cl2 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 in different pH solutions is very limited. Herein, we report a comparative study of [MnO4](-) and [MnO4·Sol](-) (Sol = H2O, KCl, and HCl) anion clusters by negative ion photoelectron spectroscopy (NIPES) and theoretical computations to probe chemical bonding and electronic structures of [MnO4·Sol](-) clusters, aimed to obtain a microscopic 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·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.