The effects of surface finishing on the corrosion behavior and electrochemical activity of AA2098-T351 (Al–Cu–Li alloy) were investigated on the basis of the correlation between surface chemistry, microstructure and electrochemical activity. The alloy was evaluated in the as-received and polished conditions. The morphology of the two types of surfaces was investigated using confocal laser scanning microscopy (CLSM), optical microscopy and optical 3D profilometry. The surface chemistry was analyzed by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). Scanning microelectrochemical techniques (namely, localized electrochemical impedance spectroscopy (LEIS), the scanning vibrating electrode technique (SVET) and scanning electrochemical microscopy (SECM) in potentiometric mode) were used to examine the electrochemical activity of the surfaces. The results showed that on the as-received surface, the near surface deformed layer (NSDL), which is composed of Mg-rich bands, influenced the corrosion activity of the alloy. Higher electrochemical activity and greater susceptibility to severe localized corrosion were related to the polished surface condition compared to the as-received one. Display omitted •Surface finishing effects on chemical activity of 2098-T351 Al–Cu–Li alloy studied using scanning microelectrochemical techniques.•The effect of the near-surface deformed layer (NSDL) on 2098-T351 Al–Cu–Li was investigated for different surface finishes.•A solid contact magnesium ion-selective microelectrode (Mg2+ ISME) employed to monitor Mg2+ distributions over the surfaces.•SVET, LEIS, and SECM in potentiometric operation produced high spatial resolution images of reactive sites on the surfaces.•The surface chemistry, microstructure and electrochemical activity of the alloy with and without NSDL were correlated.