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The addition of abundant fillers to obtain conductive and superhydrophobic waterborne polyurethane (WPU) composites generally results in increased interfaces in the composites, leading to reduced adhesion and poor corrosion resistance. Fillers such as Polytetrafluoroethylene (PTFE) and multi-walled carbon nanotubes (MWCNTs) were first treated by a coupling agent to reduce the contents of the fillers. Thus, in this work, WPU superhydrophobic conductive composites were prepared using electrostatic spraying (EsS). The polar groups (-OH and -COOH, etc.) on the WPU, PTFE, and MWCNTs were reacted with the coupling agent, making the WPU, PTFE, and MWCNTs become crosslinked together. Thus, the uniformity of the coating was improved and its curing interfaces were reduced, causing enhanced corrosion resistance. The dehydration reaction that occurred between the silane coupling agent and the polar surface of Fe formed -NH2 groups, increasing the adhesion of the coating to the steel substrate and then solving the problems of low adhesion, easy delamination, and exfoliation. With the increased content of the modified fillers, the conductivity and hydrophobic property of the composite were amplified, and its corrosion resistance and adhesion were first strengthened and then declined. The composite with the WPU, PTFE, MWCNTs, and KH-550 at a mass ratio of 7:1.5:0.1:0.032 held excellent properties; its volume resistivity and WCA were 1.5 × 104 Ω·cm and 155°, respectively. Compared with the pure WPU coating, its adhesive and anticorrosive properties were both better. This provides a foundation for the fabrication and application of anticorrosive and conductive waterborne composites.