Lithium–oxygen batteries have attracted research attention due to their low cost and high theoretical capacity. Developing inexpensive and highly efficient cathode materials without using noble metal-based catalysts is highly desirable for practical applications in lithium–oxygen batteries. Herein, a heterostructure of NiFe and NiC
x
inside of N-doped carbon (NiC
x
-NiFe-NC) derived from bimetallic Prussian blue supported on biochar was developed as a novel self-standing cathode for lithium–oxygen batteries. The specific discharge capacity of the best sample was 27.14 mAh·cm−2 at a stable discharge voltage of 2.75 V. The hybridization between the d-orbital of Ni and s and p-orbitals of carbon in NiC
x
, formed at 900 °C, enhanced the electrocatalytic performance due to the synergistic effect between these components. The structure of NiC
x
-NiFe-NC efficiently improved the electron and ion transfer between the cathode and the electrolyte during the electrochemical processes, resulting in superior electrocatalytic properties in lithium–oxygen batteries. This study indicates that nickel carbide supported on N-doped carbon is a promising cathode material for lithium–oxygen batteries.
Self-standing heterostructured NiC
x
-NiFe-NC/biochar as a highly efficient cathode for lithium–oxygen batteries