In this study, polyvinyl pyrrolidone/Ti (IV)-isopropoxide (PVP/TIP) nanofibers were obtained by electrospinning combined with sol-gel method. Then, titanium dioxide (TiO2) nanofibers were achived by appropriate heat treatment at 600 °C for 3 h. Morphology and size of the synthesized nanofibers were studied by scanning electron microscopy. The obtained results showed that long fibers with average diameter of about 60 nm were produced. Afterward, Pd/TiO2 nanofibers-carbon black (CB) catalyst has been synthesized using an in situ chemical route followed borohydride reduction method. Electrochemical investigations using cyclic voltammetry demonstrated that the Pd/TiO2 nanofibers-CB catalyst showed higher electro-catalytic activity towards ethanol oxidation than the Pd/TiO2 nanoparticles-CB catalyst in alkaline medium.