Superhydrophobic polysulfone (PSU)/carbon nanotubes (CNTs) nanocomposite coating with biomimetic golden spherical cactus surface structure (with micro-sphere and nano-thorns) was fabricated by electrostatic powder-spraying method. The superhydrophobic PSU-CNTs-FEP nanocomposite (PCFn) coating can be applied to different substrates such as aluminum plate, steel plate, glass plate, and steel pipe, which exhibited a maximum water contact angle all beyond 164 +/- 1.5 degrees and low slide angle of less than 5 +/- 0.5 degrees. The morphology, chemical composition and spherical cactus structure formation of the coatings were investigated. The electrostatic spraying and micro-phase separation promise a synergistic effect on promoting the superhydrophobicity, self-cleaning and high durability of PCFn coating. Moreover, the PCFn coating demonstrated unique multiple anti-corrosion effects, providing with air bubble corrosion protection, physical shielding and decreasing interfacial electronic agglomeration effect, which promises the wide applicability of the PCFn coatings in different engineering processes.