The use of imidazolium-based ionic liquids (ILs) as corrosion inhibitors for iron was studied using both first-principles based density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD), to understand their adsorption structure, stability, and mechanism. A total of 36 ionic liquids (ILs) were selected, with various anion type (Cl⁻, Br⁻, I⁻, N(CN)₂⁻, BF₄⁻ and PF₆⁻) and alkyl chain length (C_n, n = 0, 1, 2, 4 and 6). Our calculations revealed that the ILs exhibit strong adsorption on the metal surface and is classified as chemisorption under various different criteria. AIMD simulations including explicit solvation effects verified that these adsorption configurations calculated under vacuum are representative of the adsorption process in an aqueous environment. Furthermore, we showed that the basis of this chemisorption interaction is through net electron donation from the iron slab to the imidazolium ring. Employing dispersion corrected DFT methods (DFT-D3), we demonstrated that the alkyl chain length of the cation greatly influences adsorption energy. Finally, we showed that DFT calculations model the adsorption process much more accurately compared to classical molecular dynamics calculations. The results from this computational study agree with past experimental findings and demonstrate that DFT calculations can be used to provide insight into the nature of the adsorption process of the green and sustainable ILs involved in corrosion inhibition.