Lithium-air battery has attracted extensively attention and now developing catalysts with high electrocatalytic activity is one of the challenges for lithium-air battery. In this paper, 3D hierarchical porous spinel CoFe2O4 hollow nanospheres were first prepared by a facile hydrothermal method. The hollow CoFe2O4 nanospheres have unique bimodal porous structure which consists of micropores and mesopores. The catalytic activity of the CoFe2O4 hollow nanospheres for oxygen reduction reaction (ORR) has been studied and compared with the acetylene black, the solid CoFe2O4 nanospheres and the commercial Pt/C by using rotating ring-disk electrode (RRDE) technique. The spinel CoFe2O4 hollow nanospheres exhibit superior catalytic activity for the ORR compared to the acetylene black and the solid CoFe2O4 nanospheres. Besides, the spinel CoFe2O4 hollow nanospheres also afford high catalytic activity for the oxygen evolution reaction (OER). Furthermore, the hollow CoFe2O4 nanospheres show the smallest overpotential between ORR and OER. The chronoamperometric studies show that the CoFe2O4 hollow nanospheres exhibit excellent stability for both the ORR and OER. The high ORR and OER activities and stabilities of CoFe2O4 hollow nanospheres could be attributed to their special 3D hierarchical porous structure. This material shows a significant potential application on lithium-air battery.