A novel class of four new-free-halide-ionic liquids (ILs) derived from ammonium was synthesized and characterized via spectroscopic methods such as H-1 NMR and C-13 NMR. The synthesized compounds were evaluated as corrosion inhibitors (CIs) of API 5L X60 steel in 1 M sulfuric acid by means of the potentiodynamic polarization and weight loss techniques. The results confirmed that the inhibition efficiency displayed by the four ILs is a function of their concentration and molecular structure. The obtained inhibition efficiency (eta) ranged from 51 to 89%, confirming that the new class of ILs is good for corrosion inhibition purposes. The analysis of the potentiodynamic results showed that these compounds inhibit the corrosion of steel, classifying them as mixed-type CIs. The adsorption process of these new CIs on the API 5L X60 steel surface, which obeyed the Langmuir isotherm, was found to be physical and chemical. The SEM and EDX analyses confirmed the protection of steel in the corrosive medium.