The development of active catalyst for ethanol electrooxidation is a key to improving the power output of direct ethanol fuel cells (DEFCs). In this study, Pt-Sn was supported on SiO2 embedded carbon nanofiber as active anode catalyst for DEFC by expecting positive interactions between Pt-Sn-SiO2. The composite catalyst, Pt3Sn1/SECNF, showed highest mass activity for the ethanol electrooxidation, which was 3.7 times higher than the activity of the commercial Pt/C (Pt/Ccom). The maximum power density of DEFC single cell with the composite catalyst was 3.5 times higher than that with Pt/Ccom.