Through the development of plasma electrolytic oxidation (PEO) technology, many innovative approaches have been developed, which have enriched the PEO processes and have provided new capabilities for the PEO technique. This chapter introduces some selected new approaches, including the two-step/multi-step PEO, laser-assisted PEO, molten-salt PEO, plasma electrolytic fluoridation, ultrasound-assisted PEO, PEO in magnetic fields, cathode PEO, and scanning PEO processes, etc. These innovative PEO techniques are based on the traditional PEO theory but with different modifications of the technical routes. They have shown potential for improving property of the oxide coatings to a certain extent or have widened the application fields of the PEO technique.