Novel structure NiO-graphene foam (NiO-GF) and Ni-graphene foam (Ni-GF) were synthesized via a simple hydrothermal method combined with high-temperature calcination. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results proved that NiO and Ni nanoparticles were uniformly distributed on the reduced graphene oxide (rGO) and the particle size was about 10 nm. Graphene foam (GF) was made by rGO with a three-dimensional reticular structure. NiO-GF and Ni-GF were used as cathode catalysts for lithium-oxygen battery and showed a specific capacity performance of 25,986 mA h g−1 and 22,035 mA h g−1 at a current density of 100 mA g−1, respectively. As a three-dimensional reticular material, GF can improve the efficiency of electron transfer and provide higher surface area for NiO and Ni to grow on, which offers more active sites for catalyst. Meanwhile, NiO and Ni are capable of reducing the energy barrier of the reaction from Li and O2 to Li2O2. Three dimensional reticular material, which is made by combining rGO and NiO or Ni together, is suitable for the catalyst of lithium-oxygen battery. The research provides a new way for developing catalyst for high performance lithium-oxygen battery.