The non-polar internal cavity of β-cyclodextrin (β-CD) has been exploited for the entrapment of the hydrophobic tails of two water insoluble quaternary ammonium permanganates (QAPs): cetyltrimethylammonium permanganate (CTAP) and tetrabutylammonium permanganate (TBAP), for solubilization in aqueous medium. The solubilization and organizational behavior of the QAPs in aqueous β-CD solution have been determined from the comparison of their rates of self-oxidation in presence and in absence of β-CD. Effect of QAP concentration on their observed rate constants (k obs ) at a fixed β-CD concentration, phase solubility analysis in varying β-CD concentration, impact of quaternary ammonium bromides (QABs) on the k obs values of CTAP and TBAP at fixed QAP and β-CD concentrations, and the temperature effect have been reported. A scheme to explain the solvation of QAPs in aqueous β-CD has been proposed based on dynamic light scattering (DLS) analysis of the samples.