Reversible surface wetting behaviors between superhydrophobicity and superhydrophilicity is a hot topic research due to its potential applications in engineering. In the present work, a superhydrophilic copper film with flower-like structures was fabricated on zinc plate by a facile method of electroless deposition, and water contact angle on the copper film is 0°. After being modified by dodecanethiol (DDT), the superhydrophilic film was converted to be superhydrophobic with a water contact angle larger than 152° and a gliding angle lower than 5°. Interestingly, the superhydrophobic copper film was switched back to superhydrophilic after being annealed at 300 °C for 30 min and restored to superhydrophobic again after remodification with DDT, and the reversible switch between superhydrophobicity and superhydrophilicity could be repeated several times. Compared with the bare zinc plate and unmodified copper film, the superhydrophobic copper film modified by DDT possesses good anticorrosion properties due to the trapped air in the hierarchical structure of the “flower pits”.