The objective of this work was to determine the in-situ correlation of the elemental dissolution of Zn with the potentiodynamic polarization in deaerated and naturally aerated 1 M Na2SO4 (aq). A custom-built in-situ atomic emission spectroelectrochemistry (AESEC) electrochemical flow cell, which incorporates an inductively coupled plasma-atomic emission spectrometer (ICP-AES), was used for this purpose. Major findings include (i) O2 reduction is the dominant cathode reaction, (ii) Zn spontaneously forms a slowly dissolving oxide corrosion product film and (iii) Zn dissolution occurs under cathode polarization in the presence of dissolved O2 reduction. Postexposure imaging shows the polarized surface is covered by a solid oxide corrosion product that consists of a porous outer layer residing on a compact inner layer.