Hexaaquovanadium(II) (V(H/sub 2/O)/sub 6//sup 2 +/) is oxidized to vanadium(III) (V/sup 3 +/) by 2-propanol radicals and by ethyl ether radicals with the formation of 2-propanol and ethyl ether. The rate constants were determined by kinetic competition methods based upon the homolytic decomposition of organopentaaquochromium(III) cations. The rate constants for the respective constants are 2.1 x 10/sup 5/ and 5.9 x 10/sup 4/ M/sup -1/s/sup -1/ (at 25/sup 0/C, .1 - 1 M hydrogen ion). The mechanisms considered are (1) rate-limiting acidolysis of a seven-coordinate organovanadium species present in steady-state equilibrium with the reactants and (2) abstraction by the aliphatic radical of a hydrogen atom from a water molecule coordinated to vanadium (II). These possibilities are considered in light of data on the oxidation of 2-propanol by cobalt(III) and manganese (III). 1 figure, 2 tables.