The reactivity of the α-phase of Al-Zn (Zn-68 wt% Al, Al 5.2 Zn) in deaerated 0.1 M NaOH solution (simulating industrial pretreatments) was investigated and compared with that of pure Al and Zn. The elementary phenomena of metal oxidation, dissolution, oxide formation, and hydrogen evolution were decoupled using atomic emission spectroelectrochemistry. At the open-circuit potential, the Al 5.2 Zn phase reacted similarly as pure Al, undergoing selective Al dissolution to form a Zn(0) enriched layer. The Zn in the alloy shifted the potential to just below the onset of Zn dissolution. Elementary polarization curves showed that Zn dissolution was similar for the Al 5.2 Zn phase as for pure Zn. Near the open-circuit potential, Zn dissolution was faradaic limited by the formation of surface Zn(OH) 2 . At higher temperature, significant amounts of ZnO formed resulting in passivation. For the Al 5.2 Zn phase, the rates of Al and Zn dissolution were determined by a charge transfer mechanism across the ZnO film. Kinetic parameters (activation energies and Tafel slopes) were measured for some of the elementary processes.