This study shows the influence of the Pt percentage in Pt catalysts (Pt/C) on their application in Direct Glycerol Fuel Cells (DGFC). Catalysts with 20, 30, 40 and 60% Pt were prepared by formic acid reduction. X-Ray Diffraction (XRD) confirmed the formation of Pt fcc nanocrystals (with average sizes between 3 and 4 nm). Thermogravimetric analysis (TGA) corroborated the Pt loadings and the Transmission Electron Microscopy (TEM) images show a homogeneous distribution of the Pt nanoparticles, with larger particles at higher Pt percentages. Electrochemical measurements reveal that higher Pt percentages promote the activity of the glycerol electroxidation reaction, resulting in lower onset potentials, higher current densities and reduced poisoning of the Pt surface. Single cell tests confirm these results, with greater maximum power density at higher Pt percentages, although the glycerol crossover effect starts to become significant in the 60% Pt/C catalyst, owing to the reduced thickness of this catalytic layer. A final product selectivity analysis indicates that tartronate is the preferential glycerol electroxidation product, along with glycerate and oxalate in lower proportions, with minor amounts of glycolate and mesoxalate. In general, a thicker catalytic layer is associated with the formation of more oxidized products.