Hybrid electrocatalytic ozonation is an efficient method for degrading high-salinity organic wastewater that has excellent oxidation ability and is environmentally friendly. Furthermore, the high salt content of the wastewater provides electrolyte to support the process, which avoids secondary pollution caused by the addition of electrolyte. In this work, Ni0.2–Ce0.2/ordered mesoporous carbon (OMC)/granular active carbon (GAC) particle electrodes with a Ni:Ce weight ratio of 1:1 were synthesized using a simple method. The electrodes were characterized by transmission electron microscopy and electron paramagnetic resonance spectroscopy, as well as other techniques. The catalytic performance was investigated using cyclic voltammetry and AC impedance. Higher reduction and oxidation peak currents were obtained with the Ni0.2–Ce0.2/OMC catalyst than with Ni0.2/OMC or Ce0.2/OMC, indicating that the bimetallic catalyst has higher activity for the reduction of O2 to H2O2 and the oxidation of O3 to ·OH. The order of the k values—which represent the mass-transfer rate—was Ni0.2–Ce0.2/OMC (0.157) > Ni0.2/OMC (0.017) > Ce0.2/OMC (0.014). The results show that cooperation between Ni, Ce, and OMC promoted the dispersion of Ni and Ce and improved the catalytic performance. Ni0.2–Ce0.2/OMC enhances the catalytic reduction of O2 to H2O2, and, in addition, Ce is able to rapidly store and release oxygen through Ce3+/Ce4+ conversions and reacting with O3 to generate ·OH, which increases the oxidation capacity of the material. Under the optimal conditions the chemical oxygen demand removal for high-salinity organic wastewater using Ni0.2–Ce0.2/OMC/GAC particle electrodes reached 93.7%.