We have investigated platinum catalysts containing iron as a modifier to obtain catalysts with superior electrocatalytic activity toward glycerol electro-oxidation in an alkaline medium. The electrocatalysts, supported on carbon Vulcan, were synthesized by the polyol method. The physicochemical characterization data showed that the metals were well distributed on the carbon support and had small particle size (2 nm). The Pt:Fe metal ratio differed from the nominal composition, indicating that reducing iron with platinum was difficult, even though some parameters of the synthesis process were changed. Electrochemical analyses revealed that PtFe/C was more active and stable than commercial Pt/C was, and analysis of the electrolysis by-products showed that iron addition to Pt/C boosted the glycerol conversion and selectivity for glyceric acid formation.