We describe a coulometric method of determining the rate constants of the chemical reactions occurring in the oxidation of aliphatic alcohols by oxoammonium cations. The experiments were carried out in aqueous solutions within the pH range 4 to 5. Oxoammonium cations were generated by the electrochemical oxidation of nitroxyl radicals. The oxidation reactions of seven simple aliphatic alcohols, both primary and secondary, with different structures of the carbon chain, were examined. The values of standard rate constants of the oxidation of alcohols by oxoammonium cations were determined. The relationships between the rate of this process and the pH of the solution were also examined.