Excellent corrosion resistance is crucial for photovoltaic devices to acquire high and stable performance under high corrosive complicated environments. Creative inspiration comes from sandwich construction, whereby Fe3O4 nanoparticles were anchored onto hollow core-shell carbon mesoporous microspheres and wrapped by N-graphene nanosheets (HCCMS/Fe3O4@N-RGO) to obtain integrated high corrosive resistance and stability. The as-prepared multiple composite material possesses outstanding performance as a result of structure optimization, performance improvement, and interface synergy. Therefore, it can effectively suppress corrosion from the electrolyte in recycled tests many times, indicating the ultrahigh corrosion resistance life of this double carbon-based nanocomposite. Furthermore, the electrical conductivity and conversion efficiency of the composite are well maintained due to the triple synergistic interactions, which could serve as a guideline in establishing high-performance multifunctional HCCMS/Fe3O4@N-RGO with great prospects in energy devices, such as lithium batteries, supercapacitors and electrode materials, etc.