Palladium nanowires with a diameter of about 5 nm and length of a few tens of nanometers can be synthesized in the presence of large amount of bromide ions, employing polyvinylpyrrolidone as protective reagent while sodium borohydride as reductant. The obtained Pd nanowires are well dispersed on Vulcan XC-72 carbon. The structure and composition of the as-prepared catalyst are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectrum and inductively coupled plasma optical emission spectrometer. Electrochemical catalytic measurement results prove that the as-prepared catalyst exhibits superior electrocatalytic activity towards ethanol and formic acid electrooxidation.