Pd supported on TiO2-embedded carbon nanofibers (Pd/TECNF) were prepared as the anode catalyst for direct formic acid fuel cells (DFAFCs) using an electrospinning technique. The effect of the TiO2 content on the catalytic activity of Pd was investigated based on the electrochemical measurements of cyclic voltammetry (CV), chronoamperometry (CA), and also characterization by XRD, EDX, FE-SEM and CO stripping. The activity was significantly increased by an increase in the TiO2 content up to Ti/C=0.44 and then decreased. The maximized activity was improved eight fold by the TiO2 addition. The increased activity was attributed to the increased electrochemically active surface area due to the modified surface of the nanofibers.