The sluggish reaction kinetics at the oxygen cathode is one of the important issues hindering the commercialization of the metal-air batteries. Although the noble metal can be used as the high-efficiency electrocatalyst to solve the problems to some extent, the high cost and scarcity of these noble-metal catalysts have limited their application in electrocatalysis. In this review, we discussed the mechanisms of the ORR and OER, and proposed the principles for the bifunctional electrocatalysts firstly, and then the state-of-the-art bifunctional catalysts, including carbon-based materials and transition-metal-based materials. On the basis of that, the self-supporting 3D noble-metal-free bifunctional ORR/OER catalysts were also discussed. Finally, the perspectives for the bifunctional electrocatalysts were discussed.