Primary hydroxyl groups were oxidized regioselectively to carboxylic acid using organic nitrosonium salts generated on supported silver catalysts, which promote disproportionation of 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) in aqueous solution. The oxidation reactions were performed at pH 9.5 in a batch reactor at room temperature using heterogeneous silver catalysts and peroxides as primary co-oxidants; e.g., 99 mol% selectivity to methyl-alpha-D-glucopyrasiduronic acid was obtained at 90% conversion of the pyranoside using a silver carbonate-celite catalyst. The efficiency of the system was increased by adding carbonates to the silver catalyst. This result is explained by the increase of the electron charge deficiency on silver in the presence of carbonate, which accelerates the nucleophilic attack of hydroxyls and/or TEMPO. In the case of the Ag-Al2O3 catalyst, this result was proved by temperature-programmed desorption measurements using ammonia. With primary/secondary polyols, the selectivity for the primary hydroxyl groups is high. In addition, primary hydroxyl groups, as in the case of pyranosides, were oxidized more selectively than those of the furanosides. The observed regioselectivity is due to the sterical hindrance caused by the four methyl groups in TEMPO.