Glycerol electrooxidation reaction has been investigated by electrochemical, spectroelectrochemical, and chromatographic methods on palladium-nickel and palladium-silver nanoparticules supported on Carbon Vulcan XC 72R. These materials, prepared by the so-called "Bromide Anion Exchange" method, exhibited high activity toward the glycerol electrooxidation in alkaline medium showing furthermore an important shift of the onset potential toward low potential values. Electrolysis coupled with high-performance liquid chromatography (HPLC) and in situ Fourier transform infrared spectroscopy (FTIRS) measurements have been used to determine the various compounds generated in the oxidative conversion of this three hydroxyl groups carbon molecule. Some products with high, added value such as glycerate and tartronate have been identified. In situ FTIRS results have furthermore shown the pH decrease in the thin layer near the electrode. These results will positively serve as guidelines for future works on the potential use of glycerol in fuel cell devices in a cogeneration of high value chemicals and energy, process.