Here the binder-free nickel foam supported nitrogen-doped carbon nanotubes (N-CNTs@Ni) are synthesized by a floating catalyst chemical vapor deposition (FCCVD) method. Without any additional treatment, it could be employed as the air electrode in the lithium-oxygen batteries and delivers 1814 mAh g−1 (normalized to the weight of the air electrode) at the current density of 0.05 mA cm−2. The loose packing 3-dimension network structure facilitates the O2 diffusion in the inner electrode and provides enough void volume for the products deposition during discharge process. The improved contact between N-CNTs and the current collector Ni is beneficial to suppress the volume expansion and leads to less polarization as well as good cycling performance.