One-pot electrochemical conversion of enriched crude glycerol to higher value compounds was performed in a simple electrochemical reactor under a galvanostatic condition at an initial pH of 1 with a platinum electrode. The effect of different concentrations of hydrogen peroxide (H2O2), sodium persulfate (Na2S2O8) and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), as oxidizing agents, on the glycerol conversion and on the product distribution and yields was explored. The presence of different additives affected the concerted reaction mechanism involving the oxidant on the electrode surface, resulting in the generation of different value-added products. In the absence of an oxidizing agent, the principal reaction products was glycidol, whereas in the presence of one of H2O2, Na2S2O8 and TEMPO the main product was glycidol, ethylene glycol and 1,3-dihydroxyacetone, respectively.