The pitting potential, intrinsic surface acidity, point of zero charge of passive film on Al are studied using first-principles calculations to establish their relationships. Influences of alloying elements Zn, Cr, Nb, Si, Mo and Sc on adsorption of NH3 and NaCl, pHpzc of Al2O3 and pitting susceptibility of Al are investigated. The efficiency for enhancing pitting resistance of Al is evaluated, yielding the ratios Si: Zn: Cr: Mo: Nb: Sc = 1.8: − 0.3: 1: 1.9: 1.4: 0.2. A model for the dependence of pitting potential on the concentration of alloying elements in Al alloy matrix is developed, based on effects of alloying elements on the surface charge of passive film. The effects of Sc on pitting potential and pHpzc of Al oxide are predicted based on the calculated results, which are supported by electrochemical measurement, XPS analysis and contact angle titration.