The activation of 1,2‐diols through formation of boronate esters was found to enhance the selective oxidation of 1,2‐diols to their corresponding α‐hydroxy ketones in aqueous medium. The oxidation step was accomplished using dibromoisocyanuric acid (DBI) as a terminal chemical oxidant or an electrochemical process. The electrochemical process was based on the use of platinum electrodes, methylboronic acid [MeB(OH)2] as a catalyst and bromide ion as a mediator. Electro‐generated OH− ions (EGB) at the cathode acted as a base and “Br+” ion generated at the anode acted as an oxidant. Various cyclic and acyclic 1,2‐diols as substrates were selectively oxidized to the corresponding α‐hydroxy ketones via their boronate esters by the two oxidative methods in good to excellent yields.