A Fe/N/C oxygen reduction catalyst was prepared from polyimide nano-particles containing a low content of Fe additive. The new preparation method can provide highly active ORR catalyst but can avoid the use of HCl, which was necessary to wash out extraordinary Fe species. The kinetics was investigated in detail by the RRDE voltammetry associated with the correction of the quasi-four electron reduction, and the contribution of 2+2 electron pathway is considerable. The obtained Fe(0.5)/PI catalyst was tested in MEA and exhibited a quite promising fuel cell performance.