Coalescence-induced droplet jumping behavior (CIDJB) of superhydrophobic surfaces has a potential application in atmospheric corrosion protection by spontaneously removing the corrosive water film/droplets. However, there are few studies constructed on the zinc substrate studying the CIDJB. In addition, the effects of the complex structure characteristics on the CIDJB and the subsequent atmospheric anti-corrosion performance of the superhydrophobic surface are still lacking systematic understanding. Herein, three superhydrophobic surfaces, namely, the microstructured superhydrophobic surface, the nanostructured superhydrophobic surface, and the complex structured superhydrophobic surface were rationally prepared on the zinc surface. First, the effects of the complex structure characteristics on the CIDJB and the subsequent atmospheric corrosion protection performance of the superhydrophobic surfaces were studied. Second, the corresponding mechanism of atmospheric corrosion protection based on the CIDJB of the superhydrophobic surfaces was revealed. The results suggest that the presence of the nanostructure is an important factor for CIDJB as a result of the reduced solid-liquid contact area and interfacial adhesion. Compared with Micro SS without CIDJB, both the Nano SS and complex SS with CIDJB exhibit a better anti-corrosion performance after the simulated condensation experiments due to the jumping-induced wetting transformation mechanism. This study provides criteria for designing efficient anti-corrosion materials based on the CIDJB.