By pyrolyzed the products from hydrothermal reaction of 1, 4, 5, 8-naphthalene tetramethyl anhydride, NaOH and FeSO 4 , the nanoparticles of FeFe 2 O 4 were produced, and then its electrochemical performance of oxygen reduction reaction (ORR) was evaluated in O 2 saturated 0.1 M KOH solution. The results indicated that, among all the as-prepared samples, FeFe 2 O 4 -0.50 was mainly composed of uniformly dispersed spherical nanoparticles of 20-30nm and behaved the best ORR catalytic performance. Its half-wave potential and limiting diffusion current density was 0.61 V and À 1.85 mA cm À 2 @0.4 V vs. RHE), respectively, higher about 20 mV and 1.29 mA cm À 2 than that of FeFe 2 O 4 (0.59 V and À 0.56 mA cm À 2 @0.4 V vs. RHE). In addition, FeFe 2 O 4 -0.50 also showed stronger stability as well as methanol/CO tolerance than that of commercial 20 % Pt/C. It was the evenly dispersed FeFe 2 O 4 nanoscale and FeÀ O bond in FeFe 2 O 4 -0.50 that contributed its excellent electrochemical performance and tolerance for CO and methanol. The asprepare FeFe 2 O 4 -0.50 might be a potential alternative catalyst for ORR in fuel cell.