The practical application of Pt-based technologies depends on the lowering in the costs and one way to face this challenge is by reducing the amount of Pt. Herein, we decorate Ag nanoparticles with ultra-small (0.8 %) quantities of Pt and test them for the electrooxidation of glycerol. We showed that the Pt atoms of our catalyst are one order of magnitude more active (in terms of mass activity) than Pt/C commercial catalyst. By performing in situ FTIR measurements, electrolysis experiments and HPLC analysis, we showed that both catalysts form mainly glycerate and lactate, but Pt/C is more prone to poisoning and to form carbonate. We suggest that this different behavior is attributed to the high dispersion of the Pt atoms on Ag nanoparticles. The lower probability of finding neighboring Pt atoms diminishes the formation of multiple bonded intermediates, which are precursors for the formation of carbonate and some poisoning intermediates.