The kinetics of oxidation of 1-octene and heptanal by 18-crown-6-ether-solubilized KMnO4 in benzene and CH2Cl2 have been investigated. In benzene, the oxidation of 1-octene is first order with respect to the oxidant and zero order with respect to the substrate, whereas in CH2Cl2 the reaction is first order with respect to both substrate and oxidant. The reaction of heptanal followed different kinetics being first order with respect to both substrate and oxidant, regardless of whether benzene or CH2Cl2 was employed as the solvent. The values of activation energy E a, standard enthalpy ΔH *, standard entropy change ΔS *, and standard free energy ΔG *, for the reaction, are reported. Mechanistic pathways for the studied reactions are also proposed.