Corrosion protection of aluminum in 2 mol/L HSO solution is examined in the presence of ortho-substituted aniline derivatives using potentiodynamic polarization and electrochemical impedance spectroscopy measurements. Density function theory (DFT) calculations are performed to investigate the aluminum-electrolyte interface relationship in the absence and presence of both ortho-substituted aniline derivatives and sulphate anions, as well as their roles in the protection efficiency at the atomic level. Our results show that ortho-aniline derivatives are good inhibitors and that their efficiencies improved as the concentration increased. SEM-EDX analysis is used to confirm the adsorption thermodynamics of the studied compounds on the aluminum surface. The best inhibitory effect is exhibits in the presence of the methyl group in ortho-position followed by ortho-carboxilic compared to aniline. The adsorption of these compounds on the aluminum surface is well described by Langmuir adsorption isotherm as well as the experimental and the theoretical adosrption energies are in a good agreement. DFT calculations also show that the interaction between the inhibitors and the aluminum surface is mainly electrostatic and depends on the type of the ortho-substituted group in addition to the sulphate anions.