Brush electrodeposition of Ni/PTFE composite coatings was explored using a nickel high speed solution and polytetrafluoroethylene (PTFE) particles 6–9 μm in diameter. A novel bilayer-like, partially intercalated structure was produced, consisting of a rough nickel sublayer covered by an outer, compact, smooth PTFE layer. The study of the coating growth revealed that the PTFE particles bind together on the nickel coating valleys and grow until all the surface is covered by a polymer layer without the need of a baking stage. The resulting coating presents a hydrophobic surface with a low coefficient of friction (0.10) and higher corrosion resistance to salt spray testing than the nodular nickel coating. The coatings were produced using an aqueous nickel plating solution, where the hydrophobic PTFE particles were suspended using different substances: cetrimonium bromide (CTAB) cationic surfactant, isopropyl alcohol premixed with the particles, and ethanol premixed with the particles. High concentrations of the suspending products were detrimental for the deposition process, but optimal values of 0.1 g/l, 3 ml/l and 3 ml/l respectively were found. All compounds successfully suspended the PTFE particles and both alcohols produced the Ni/PTFE coating described before, but the CTAB failed to co-deposit the polymer.