To improve the electrocatalytic properties for an ethanol electro-oxidation reaction, modifications of Pt nanocrystallites have been used by alloying with other elements such as Ru, Sn, and Au. Here we demonstrate carbon supported Pt3Sn alloy electrocatalyst (Pt3Sn/C) synthesized using a thermal-decomposition method. The PtSn/C prepared by the present synthetic process shows a homogeneous distribution of ultrasmall alloy nanoparticles (∼2.5 nm) in the presence of Pt and Sn metallic states. At 0.45 V, the Pt3Sn/C (0.35 mA cm−2) exhibits much higher current density as compared with Pt/C (0.13 mA cm−2). In an electrochemical stability test, the Pt3Sn/C supported quite high current density and thus showed 3% current reduction after the stability test.